Theoretical Study of Solvent Effects on the Cis-To-Transisomerization of Pd(C6cl2f3)I(PH3)2

Supplementary Material for:

Theoretical Study of Solvent Effects on the Cis-to-TransIsomerization of [Pd(C6Cl2F3)I(PH3)2]

Ali Morsali ·FatemehHoseinzade ·AlirezaAkbari ·S. Ali Beyramabadi · Reza Ghiasi

A. Morsali · S.A.Beyramabadi

Department of Chemistry, Mashhad Branch, Islamic Azad University, Mashhad, Iran

FatemehHoseinzade ·

Technical and Vocational University, Tehran, Iran

AlirezaAkbari()

Department of Chemistry, Faculty of Sciences, PayameNoor University, Iran

e-mail: ; tel./fax: 00985118683873

R. Ghiasi

Department of Chemistry, Basic Science Faculty, East Tehran Branch of East Tehran, Islamic Azad University, QiamDasht, Tehran, Iran

XYZ coordinates, absolute electronic energies (E). and Gibbs energies (G) for allcomputed structures. The atomic unit (a.u.) of energy, the hartree, is equal to 4.359744  10–18 J

A)Solvent phase

Table S1Structure tsB2 (in acetone):

Pd -1.61348 -0.63767 -0.89260

I -2.99161 -2.53613 0.56758

P -1.95116 -2.44836 -3.35690

H -1.78159 -3.82725 -3.07257

H -1.54618 -2.54534 -4.71739

H -3.33971 -2.54060 -3.62985

P -0.65909 1.08529 -2.10005

H -1.52806 1.93313 -2.81099

H 0.24378 0.71344 -3.11251

H 0.10550 2.02481 -1.38621

C -2.92103 0.75364 -0.23741

C -4.09281 1.06219 -0.91770

C -2.69048 1.43189 0.95400

C -5.01842 1.99622 -0.44304

C -3.58262 2.37469 1.47218

C -4.75061 2.64806 0.76050

F -1.56598 1.18132 1.65359

F -5.61939 3.54663 1.23458

F -4.36518 0.44456 -2.08260

Cl -3.25659 3.19801 2.97022

Cl -6.47688 2.34863 -1.32401

Pd 2.19788 -0.67861 1.52908

C 3.46454 0.47049 0.37683

C 4.72411 0.01879 0.00446

C 3.08799 1.71531 -0.10737

C 5.58195 0.74903 -0.82290

C 3.90061 2.49235 -0.93730

C 5.15405 1.99204 -1.29056

P 3.20586 0.38475 3.30773

H 2.79581 0.06741 4.61605

H 4.59625 0.20550 3.40655

H 3.10747 1.78679 3.32525

P 0.73682 -2.06525 2.83858

H 1.10936 -3.42127 2.91053

H 0.54466 -1.79522 4.20932

H -0.59648 -2.18535 2.39733

I 1.21538 -1.91943 -0.75250

F 5.15275 -1.17854 0.45301

F 1.87563 2.21272 0.22797

F 5.95409 2.71185 -2.08312

Cl 7.14920 0.13856 -1.26832

Cl 3.38013 4.04635 -1.52225

PCM model: E = -4545.845182 a.u., G = -4545.929895a.u.

Table S2Structure A(in acetone):

Pd -1.11688 -0.37209 -0.44135

I -1.33458 2.03189 0.87762

C 0.87609 -0.30875 -0.21189

C 1.50494 -0.84299 0.90676

C 1.69461 0.30544 -1.15301

C 2.88646 -0.77187 1.10659

C 3.08074 0.40361 -1.00376

C 3.66752 -0.14095 0.13848

P -0.80100 -2.41546 -1.50014

H -0.20587 -3.44628 -0.75042

H -1.95456 -3.06450 -1.98132

H 0.01229 -2.43076 -2.64794

F 1.14154 0.83759 -2.25960

F 0.76350 -1.45578 1.84990

F 4.99150 -0.06053 0.30528

Cl 3.62836 -1.44949 2.52678

Cl 4.06426 1.18583 -2.20683

O -3.27048 -0.40281 -0.83757

C -4.21198 -0.78054 -0.12910

C -3.99954 -1.36415 1.23911

H -3.71879 -2.41814 1.11568

H -3.17778 -0.85510 1.74775

H -4.90696 -1.32520 1.84405

C -5.61397 -0.67433 -0.65287

H -6.12700 -1.63609 -0.54463

H -6.16623 0.04748 -0.03907

H -5.61953 -0.35351 -1.69461

PCM model: E = -2122.890096a.u., G = -2122.946372a.u.

Table S3Structure 2···2(in acetone):

Pd 3.00588 -1.49373 0.62227

I 4.09685 -2.10845 -1.83725

P 1.88057 -3.61279 0.56344

H 2.70619 -4.75334 0.54709

H 0.98083 -3.98398 1.58550

H 1.08128 -3.86763 -0.56531

P 2.22767 -0.81995 2.69077

H 3.21363 -0.60204 3.66979

H 1.54232 0.40670 2.72232

H 1.33198 -1.64585 3.39614

C 4.00451 0.30692 0.61839

C 3.43440 1.45801 0.09192

C 5.30153 0.42555 1.10032

C 4.10647 2.68135 0.02310

C 6.02453 1.62124 1.05862

C 5.41123 2.74869 0.51206

F 5.90706 -0.65473 1.63460

F 6.07821 3.90645 0.46025

F 2.17004 1.40781 -0.38052

Cl 7.65143 1.71886 1.66990

Cl 3.35017 4.09706 -0.65111

Pd -2.99222 1.09383 -1.18072

C -4.62849 0.46871 -0.10065

C -4.87341 0.94310 1.18105

C -5.51597 -0.48015 -0.59042

C -5.93971 0.49815 1.96756

C -6.59955 -0.96297 0.14903

C -6.79967 -0.46320 1.43602

P -4.43144 2.69756 -2.01494

H -4.95461 3.59897 -1.07085

H -3.97831 3.58585 -3.00882

H -5.61157 2.21418 -2.60639

P -1.03516 1.78110 -2.39655

H -0.50103 0.83934 -3.29589

H -1.07023 2.91761 -3.23190

H 0.11016 2.07250 -1.63403

I -1.49458 -0.94151 -0.07568

F -4.05213 1.87580 1.70565

F -5.33725 -0.96929 -1.83451

F -7.82791 -0.90742 2.16624

Cl -6.20290 1.11773 3.57280

Cl -7.68229 -2.15879 -0.50468

PCM model: E =-4545.866546a.u.,G =-4545.952602a.u.

Table S4Structure B (in acetone):

Pd -1.39220 -0.26651 -0.68622

I -2.51524 -2.69609 -0.01614

C -3.13507 0.60417 -0.14185

C -3.36744 1.01184 1.16585

C -4.16753 0.79836 -1.05123

C -4.57555 1.58116 1.57761

C -5.39498 1.36331 -0.69322

C -5.58768 1.75095 0.63274

P -0.72788 1.88991 -1.20586

H -0.86096 2.86242 -0.19914

H 0.59253 2.11908 -1.63234

H -1.45132 2.50062 -2.24706

F -2.39856 0.85503 2.08857

F -6.75206 2.29509 1.00068

F -3.99406 0.43017 -2.33531

Cl -4.82564 2.07206 3.22805

Cl -6.66244 1.58536 -1.86416

Pd 2.53787 -1.41318 0.79713

P 3.77253 -1.25626 2.73405

H 3.46232 -0.15858 3.55469

H 3.72572 -2.31502 3.65912

H 5.15826 -1.09685 2.56557

C 3.39607 0.40904 0.36116

C 2.76507 1.61446 0.63553

C 4.63684 0.48826 -0.25855

C 3.31950 2.85737 0.31683

C 5.24112 1.70002 -0.60493

C 4.56688 2.88469 -0.30817

P 1.57527 -3.56740 1.26062

H 0.17089 -3.64615 1.17401

H 1.95382 -4.59613 0.37745

H 1.80923 -4.20443 2.49647

F 1.54994 1.60319 1.22890

F 5.30283 -0.64991 -0.54161

F 5.12152 4.05833 -0.62445

Cl 2.49383 4.34336 0.68661

Cl 6.79601 1.74772 -1.38280

I 1.10317 -1.37232 -1.59094

PCM model: E =-4202.733231a.u., G =-4202.813923a.u.

Table S5Structure ts A2 (in acetone):

Pd 0.96513 -0.19938 -0.50917

I 1.07620 -0.71054 2.19861

P 2.82195 -2.43114 -1.03736

H 3.81183 -2.55912 -0.03302

H 3.70434 -2.62998 -2.13259

H 2.37605 -3.77640 -0.97349

P 0.68740 0.29272 -2.74647

H 1.86917 0.38182 -3.50663

H -0.06326 -0.61154 -3.51995

H 0.05772 1.50413 -3.08784

C -1.02568 0.04405 -0.35503

C -1.90343 -1.02919 -0.45920

C -1.58919 1.28982 -0.10236

C -3.28632 -0.89328 -0.30739

C -2.96454 1.48040 0.05852

C -3.80687 0.37376 -0.04524

F -0.79199 2.37202 -0.00393

F -5.12617 0.52979 0.10338

F -1.41874 -2.25909 -0.71217

Cl -3.62647 3.05696 0.38095

Cl -4.34745 -2.26567 -0.44055

C 3.77575 1.71947 -0.33759

C 5.25292 1.99019 -0.47912

H 5.78241 1.08486 -0.77775

H 5.66079 2.37284 0.46240

H 5.40803 2.77163 -1.23218

C 2.91918 2.82553 0.22093

H 1.85881 2.61239 0.08314

H 3.18161 3.78500 -0.23527

H 3.12548 2.91731 1.29438

O 3.31374 0.62656 -0.66527

PCM model: E =-2465.999374a.u.,G =-2466.063633a.u.

Table S6Structure PH3 (in acetone):

P 0.00000 0.00000 0.12643

H 0.00000 1.20117 -0.63214

H -1.04024 -0.60059 -0.63214

H 1.04024 -0.60059 -0.63214

PCM model: E =-343.122468a.u., G =-343.142469a.u.

Table S7Structure 2 (in acetone):

Pd -1.41866 0.69039 0.16876

I -1.84187 -1.94694 -0.51075

P -3.80192 0.96517 0.25415

H -4.49111 0.13016 1.15315

H -4.37966 2.20790 0.59041

H -4.50698 0.68682 -0.93163

P -0.84652 2.86094 0.72439

H -0.02116 3.52955 -0.19670

H -1.85753 3.82108 0.92164

H -0.10270 3.01259 1.90797

C 0.61438 0.37925 0.09581

C 1.34620 0.57610 -1.06729

C 1.31713 -0.08526 1.19944

C 2.71680 0.31662 -1.15806

C 2.68668 -0.36260 1.16893

C 3.37846 -0.15737 -0.02512

F 0.66141 -0.28570 2.36061

F 4.68957 -0.41352 -0.08320

F 0.71985 1.03775 -2.16911

Cl 3.52381 -0.95018 2.57744

Cl 3.59196 0.57388 -2.64056

PCM model: E =-2272.932478a.u., G =-2272.982844a.u.

Table S8Structure Ac (in acetone):

C 0.00000 0.18142 -0.00001

C 1.28978 -0.61391 -0.00138

H 1.36583 -1.20045 0.92151

H 1.30068 -1.32834 -0.83161

H 2.14635 0.05727 -0.07746

C -1.28974 -0.61397 0.00137

H -1.36568 -1.20071 -0.92139

H -1.30069 -1.32819 0.83179

H -2.14636 0.05718 0.07724

O -0.00005 1.40275 0.00000

PCM model: E =-193.085977a.u., G =-193.113986a.u.

Table S9Structure 2···Ac (in acetone):

Pd -0.84778 -0.58072 0.55108

I -0.35692 -2.50019 -1.37155

P -3.04224 -1.50436 0.83383

H -3.09575 -2.88551 1.10502

H -3.90189 -1.02401 1.84061

H -3.89790 -1.43890 -0.27965

P -1.08476 1.07719 2.14060

H -1.01509 2.39935 1.67327

H -2.24812 1.11840 2.92722

H -0.08595 1.09111 3.13149

C 1.03880 0.19203 0.27440

C 1.29881 1.16295 -0.68324

C 2.12887 -0.26285 1.00386

C 2.57920 1.66533 -0.93289

C 3.43164 0.20089 0.79995

C 3.64429 1.17077 -0.17986

F 1.93842 -1.19882 1.95711

F 4.88033 1.63362 -0.39657

F 0.27897 1.65320 -1.41770

Cl 4.76774 -0.40536 1.73748

Cl 2.85601 2.87940 -2.14993

C -4.40389 2.40096 -0.03183

C -5.60701 2.01006 -0.85996

H -5.47580 2.35153 -1.89294

H -5.74587 0.92831 -0.84605

H -6.50592 2.50492 -0.47609

C -4.09677 3.87773 0.07425

H -3.91643 4.29432 -0.92308

H -4.95841 4.41256 0.48879

H -3.22209 4.04308 0.70462

O -3.70975 1.55974 0.52636

PCM model: E =-2466.020216a.u., G =-2466.085748a.u.

Table S10Structure B···PH3 (in acetone):

Pd -1.27386 -0.28703 -0.49256

I -2.27465 -2.85989 -0.42867

C -3.01313 0.33506 0.33329

C -3.18349 0.39305 1.71099

C -4.10411 0.69780 -0.44676

C -4.38457 0.78255 2.30987

C -5.32840 1.09380 0.09893

C -5.45603 1.13126 1.48745

P -0.70049 1.95507 -0.46268

H -0.85351 2.64016 0.75560

H 0.60675 2.32666 -0.82464

H -1.46043 2.77068 -1.32343

F -2.15741 0.05848 2.51756

F -6.61566 1.50815 2.03557

F -3.99556 0.66364 -1.79110

Cl -4.55492 0.83645 4.04065

Cl -6.67222 1.53105 -0.91573

Pd 2.76415 -1.57117 0.45202

P 4.13981 -1.84737 2.27872

H 3.86103 -1.01109 3.37301

H 4.19939 -3.10698 2.90226

H 5.50216 -1.58103 2.06187

C 3.51624 0.34851 0.44368

C 2.87775 1.40350 1.08049

C 4.68900 0.65525 -0.23477

C 3.36035 2.71535 1.05799

C 5.21919 1.94687 -0.29702

C 4.54064 2.97373 0.35985

P 1.91511 -3.81937 0.41222

H 0.51359 -3.94536 0.33438

H 2.31341 -4.59439 -0.69352

H 2.21291 -4.71435 1.46017

F 1.72586 1.17009 1.74902

F 5.36063 -0.33079 -0.86376

F 5.02643 4.21775 0.32092

Cl 2.52753 4.00466 1.87696

Cl 6.68976 2.28237 -1.16309

I 1.18400 -1.01271 -1.77009

P -3.29162 3.25606 -3.86308

H -2.99646 2.05226 -4.55690

H -3.22288 4.06906 -5.02728

H -4.69904 3.08094 -3.93722

PCM model: E =-4545.853869a.u., G =-4545.945059a.u.

Table S11Structure A···PH3 (in acetone):

Pd 1.16870 0.30486 0.30568

I 1.63453 -1.35563 -1.84025

C -0.77221 -0.20284 0.27405

C -1.23885 -1.31699 0.96287

C -1.71176 0.51372 -0.45806

C -2.57438 -1.72641 0.92835

C -3.05904 0.14837 -0.52896

C -3.47951 -0.98169 0.17205

P 0.62785 1.68355 2.09341

H 0.02420 1.09027 3.21677

H 1.69160 2.38298 2.69597

H -0.27234 2.73202 1.82292

F -1.32087 1.61080 -1.13894

F -0.37602 -2.04557 1.69697

F -4.76292 -1.35235 0.12198

Cl -3.10972 -3.13156 1.80299

Cl -4.19708 1.06972 -1.46801

O 3.26659 0.96996 0.29893

P -1.78510 4.78543 -0.00132

H -3.02177 4.39694 -0.58108

H -1.10624 4.87780 -1.24548

H -2.11525 6.16733 0.04356

C 4.27597 0.43254 0.77079

C 4.20805 -0.86323 1.52807

H 5.12701 -1.06809 2.07885

H 3.35001 -0.86108 2.20559

H 4.04568 -1.66685 0.79913

C 5.61638 1.07379 0.56241

H 6.04510 1.33785 1.53629

H 6.30124 0.35064 0.10523

H 5.53246 1.96262 -0.06290

PCM model: E =-2466.010935a.u., G =-2466.07862a.u.

Table S12Structure ts B2(in DMF):

Pd -1.61224 -0.72397 -0.83863

I -3.04397 -2.49950 0.72773

P -1.85262 -2.76308 -3.19049

H -1.66046 -4.10698 -2.77931

H -1.39579 -2.97052 -4.52171

H -3.22747 -2.92035 -3.50312

P -0.62115 0.88256 -2.17036

H -1.46748 1.70727 -2.93386

H 0.26004 0.40826 -3.15852

H 0.18166 1.84159 -1.52860

C -2.92673 0.71933 -0.33038

C -4.08876 0.97558 -1.04770

C -2.70670 1.49201 0.80437

C -5.01511 1.94900 -0.66175

C -3.59977 2.47750 1.23344

C -4.75801 2.69610 0.48758

F -1.59063 1.29462 1.53556

F -5.62812 3.63349 0.87655

F -4.35163 0.26542 -2.16090

Cl -3.28764 3.41906 2.66305

Cl -6.46232 2.23323 -1.58494

Pd 2.10142 -0.39641 1.59724

C 3.48374 0.49476 0.35156

C 4.72492 -0.08464 0.11909

C 3.21899 1.67556 -0.32779

C 5.66817 0.45882 -0.75723

C 4.12058 2.26738 -1.21673

C 5.35022 1.64247 -1.42418

P 2.99193 1.00432 3.19835

H 2.47498 0.96938 4.50677

H 4.36758 0.85599 3.44314

H 2.90818 2.37653 2.90741

P 0.52972 -1.47558 3.05616

H 0.93866 -2.73450 3.53778

H 0.16777 -0.85996 4.27163

H -0.73751 -1.79606 2.52927

I 1.19644 -1.97544 -0.50432

F 5.04934 -1.22572 0.76028

F 2.03517 2.30004 -0.12866

F 6.23418 2.18497 -2.26723

Cl 7.20742 -0.30849 -1.02104

Cl 3.73810 3.74780 -2.04734

PCM model: E =-4545.846641a.u., G =-4545.933111a.u.

Table S13Structure 2···2(in DMF):

Pd 3.14731 -1.45274 0.61893

I 4.26946 -2.04624 -1.83349

P 1.99754 -3.55720 0.51833

H 2.80991 -4.70597 0.47095

H 1.10192 -3.93870 1.53921

H 1.18631 -3.77936 -0.60935

P 2.34674 -0.79652 2.68386

H 3.32335 -0.59361 3.67489

H 1.66604 0.43265 2.72060

H 1.43992 -1.62746 3.36859

C 4.16807 0.33418 0.65923

C 3.62784 1.49474 0.12188

C 5.44986 0.43348 1.18369

C 4.31698 2.71026 0.08516

C 6.18775 1.62071 1.17516

C 5.60538 2.75915 0.61776

F 6.02503 -0.65858 1.72828

F 6.28701 3.90953 0.59665

F 2.38256 1.46299 -0.39491

Cl 7.79494 1.69419 1.84019

Cl 3.59963 4.13883 -0.60451

Pd -3.45925 0.90188 -1.52118

C -4.78312 0.38526 -0.03351

C -4.90949 1.13206 1.12981

C -5.56395 -0.75914 -0.12369

C -5.76009 0.77084 2.17865

C -6.43199 -1.17075 0.89142

C -6.51972 -0.39154 2.04549

P -5.20456 2.18802 -2.32124

H -5.68341 3.16933 -1.43579

H -5.02943 2.94632 -3.49412

H -6.39076 1.49687 -2.62432

P -1.86491 1.44851 -3.23394

H -1.33065 0.36353 -3.95365

H -2.21211 2.29979 -4.30400

H -0.67687 2.07153 -2.80828

I -1.52489 -0.67800 -0.34385

F -4.18391 2.26072 1.26922

F -5.49006 -1.52027 -1.23453

F -7.34282 -0.76103 3.03252

Cl -5.88121 1.73673 3.62165

Cl -7.38774 -2.61731 0.73624

PCM model: E =-4545.867448a.u., G =-4545.959381a.u.

Table S14Structure B···PH3(in DMF):

Pd -1.27595 -0.28879 -0.49018

I -2.28146 -2.86242 -0.42962

C -3.01461 0.33761 0.33410

C -3.18545 0.39811 1.71165

C -4.10503 0.70057 -0.44663

C -4.38617 0.79011 2.30964

C -5.32892 1.09911 0.09801

C -5.45685 1.13915 1.48640

P -0.69840 1.95172 -0.46044

H -0.84848 2.63643 0.75827

H 0.60939 2.31890 -0.82432

H -1.45762 2.76876 -1.32022

F -2.16026 0.06291 2.51919

F -6.61624 1.51825 2.03360

F -3.99665 0.66323 -1.79106

Cl -4.55704 0.84650 4.04030

Cl -6.67206 1.53610 -0.91779

Pd 2.76970 -1.57130 0.45522

P 4.15471 -1.84409 2.27532

H 3.87575 -1.01165 3.37234

H 4.22352 -3.10515 2.89452

H 5.51417 -1.56936 2.05177

C 3.51800 0.34976 0.44225

C 2.88030 1.40305 1.08271

C 4.68673 0.65968 -0.24166

C 3.36024 2.71584 1.05942

C 5.21386 1.95247 -0.30528

C 4.53665 2.97727 0.35602

P 1.92389 -3.82082 0.42700

H 0.52247 -3.94983 0.35541

H 2.31797 -4.59966 -0.67757

H 2.22648 -4.71144 1.47699

F 1.73151 1.16706 1.75574

F 5.35733 -0.32411 -0.87539

F 5.01979 4.22245 0.31590

Cl 2.52875 4.00279 1.88359

Cl 6.67941 2.29200 -1.17865

I 1.18088 -1.01963 -1.76563

P -3.28201 3.24458 -3.87828

H -4.68272 3.04210 -3.99729

H -2.94162 2.03812 -4.54631

H -3.18922 4.04432 -5.04989

PCM model: E =-4545.855264a.u.,G =-4545.94626a.u.

Table S15Structure A···PH3(in DMF):

Pd -0.85345 -0.23053 -0.52273

I -1.09893 -0.15921 2.22336

C 1.14410 -0.35050 -0.34786

C 1.80181 -1.57530 -0.31890

C 1.94154 0.78253 -0.23481

C 3.18754 -1.69208 -0.17917

C 3.33071 0.72483 -0.09236

C 3.94549 -0.52686 -0.06563

P -0.53521 -0.32409 -2.81567

H 0.02460 -1.50123 -3.34561

H -1.69876 -0.19944 -3.59827

H 0.29780 0.64277 -3.40746

F 1.36382 2.00023 -0.25481

F 1.08449 -2.71107 -0.43088

F 5.27339 -0.61098 0.06712

Cl 3.96396 -3.24905 -0.14985

Cl 4.28470 2.17309 0.05137

N -5.16221 -0.65446 -0.50477

C -6.11883 -1.53524 0.15996

H -5.58855 -2.26375 0.77465

H -6.78787 -0.94954 0.79780

H -6.71779 -2.06660 -0.58571

C -5.70686 0.38120 -1.37998

H -6.37219 1.03512 -0.80804

H -4.88729 0.96463 -1.79444

H -6.27777 -0.08171 -2.19047

C -3.85249 -0.78005 -0.30247

H -3.56681 -1.57895 0.38865

O -2.99159 -0.04609 -0.84566

P -0.06953 5.09675 -0.31828

H 1.28756 5.04538 0.10180

H -0.56962 4.53277 0.88604

H -0.26246 6.43990 0.10497

PCM model: E =-2521.354963a.u., G =-2521.427469a.u.

Table S16Structure B(in DMF):

Pd -1.39307 -0.26901 -0.68591

I -2.51903 -2.70016 -0.01605

C -3.13472 0.60507 -0.14260

C -3.36634 1.01551 1.16440

C -4.16743 0.79880 -1.05177

C -4.57376 1.58669 1.57561

C -5.39419 1.36554 -0.69443

C -5.58599 1.75595 0.63081

P -0.72607 1.88596 -1.20555

H -0.85956 2.85826 -0.19889

H 0.59564 2.11098 -1.62961

H -1.44709 2.49632 -2.24841

F -2.39753 0.85907 2.08735

F -6.74987 2.30163 0.99823

F -3.99524 0.42744 -2.33530

Cl -4.82296 2.08045 3.22537

Cl -6.66210 1.58623 -1.86525

Pd 2.54056 -1.41195 0.79996

P 3.77718 -1.24999 2.73492

H 3.46833 -0.14986 3.55252

H 3.72898 -2.30706 3.66153

H 5.16269 -1.09273 2.56362

C 3.39577 0.41056 0.35990

C 2.76613 1.61597 0.63749

C 4.63383 0.49013 -0.26513

C 3.31957 2.85903 0.31767

C 5.23682 1.70202 -0.61312

C 4.56432 2.88660 -0.31237

P 1.58442 -3.56721 1.27279

H 0.17979 -3.64959 1.19667

H 1.95795 -4.59635 0.38799

H 1.82820 -4.20223 2.50751

F 1.55316 1.60467 1.23532

F 5.29832 -0.64789 -0.55254

F 5.11801 4.06046 -0.63010

Cl 2.49588 4.34499 0.69223

Cl 6.78836 1.75005 -1.39809

I 1.10158 -1.37765 -1.58885

PCM model: E =-4202.734669a.u., G =-4202.815564a.u.

Table S17Structure PH3(in DMF):

P 0.00000 0.00000 0.12635

H 0.00000 1.20135 -0.63176

H -1.04040 -0.60067 -0.63176

H 1.04040 -0.60067 -0.63176

PCM model: E =-343.122527a.u., G =-343.142528a.u.

Table S18Structure ts A2(in DMF):

Pd 0.73032 -0.39851 -0.46816

I 0.66608 -1.27917 2.14859

C -1.21350 0.09656 -0.31710

C -1.59394 1.38143 0.05538

C -2.23913 -0.80835 -0.56575

C -2.92992 1.76884 0.19056

C -3.59080 -0.47131 -0.44956

C -3.92540 0.82670 -0.06554

P 0.59923 0.42548 -2.62003

H 0.47896 1.82187 -2.75312

H 1.69919 0.17455 -3.46126

H -0.46599 -0.00125 -3.43284

P 2.49257 -2.63465 -1.32032

H 2.14701 -3.96998 -1.65464

H 3.45015 -2.47772 -2.35587

H 3.42833 -2.97878 -0.31485

F -0.64579 2.30813 0.29967

F -5.21165 1.17175 0.05475

F -1.93951 -2.06667 -0.93845

Cl -3.35717 3.38782 0.66395

Cl -4.84087 -1.63881 -0.76888

N 4.60620 1.95432 -0.06991

C 4.83064 3.33714 0.33606

H 3.88157 3.80400 0.60472

H 5.49983 3.37332 1.20163

H 5.28596 3.90440 -0.48238

C 5.77719 1.17298 -0.45361

H 5.45888 0.16769 -0.72341

H 6.48332 1.12369 0.38143

H 6.27673 1.64207 -1.30749

C 3.37543 1.42559 -0.09404

H 2.58656 2.12212 0.22138

O 3.10851 0.25617 -0.43082

PCM model: E =-2521.341319a.u., G =-2521.408826a.u.

Table S19 Structure DMF(in DMF):

N 0.34267 -0.01996 -0.00034

C 1.59410 -0.76040 0.00000

H 1.38838 -1.83282 -0.00022

H 2.18821 -0.51748 -0.88833

H 2.18758 -0.51771 0.88883

C 0.41939 1.43325 0.00009

H 0.95275 1.78951 -0.88836

H -0.59491 1.83050 -0.00042

H 0.95165 1.78899 0.88943

C -0.85716 -0.64907 0.00019

H -0.74953 -1.74887 0.00046

O -1.95760 -0.09938 -0.00009

PCM model: E =-248.426717a.u., G =-248.455802a.u.

Table S20 Structure 2(in DMF):

Pd -1.41661 0.70914 -0.00023

I -1.85497 -2.01390 0.00016

C 0.61597 0.38251 -0.00022

C 1.33468 0.24722 -1.18053

C 1.33439 0.24756 1.18033

C 2.70571 -0.02351 -1.21172

C 2.70540 -0.02318 1.21193

C 3.38307 -0.15873 0.00021

P -0.84208 2.94670 -0.00047

H -0.05756 3.37666 -1.08493

H -1.85772 3.92140 -0.00135

H -0.05925 3.37681 1.08515

P -3.79401 1.02290 0.00009

H -4.49966 0.45811 -1.07872

H -4.49919 0.45890 1.07961

H -4.35002 2.31947 -0.00026

F 0.69487 0.37921 -2.36071

F 4.69512 -0.41730 0.00041

F 0.69433 0.37994 2.36033

Cl 3.56234 -0.18996 -2.71800

Cl 3.56167 -0.18925 2.71846

PCM model: E =-2272.933596a.u., G =-2272.984989a.u.

Table S21 Structure A(in DMF):

Pd -0.85697 -0.53850 -0.03973

I -1.07984 2.19894 -0.29466

C 1.14187 -0.36007 0.02674

C 1.81904 -0.19665 1.22997

C 1.91995 -0.38382 -1.12503

C 3.20696 -0.05022 1.30673

C 3.31041 -0.24270 -1.10619

C 3.94574 -0.07461 0.12405

P -0.52749 -2.82581 0.11226

H -0.02753 -3.33369 1.32584

H -1.68110 -3.61400 -0.06062

H 0.35854 -3.42602 -0.80032

F 1.32125 -0.54892 -2.32056

F 1.12041 -0.17303 2.38193

F 5.27497 0.06422 0.17038

Cl 4.00898 0.15662 2.83728

Cl 4.24040 -0.27310 -2.57664

N -5.20730 -0.48957 0.21937

C -6.23104 0.42582 0.71563

H -5.76318 1.32852 1.11074

H -6.91052 0.70244 -0.09630

H -6.80922 -0.05452 1.51101

C -5.66647 -1.75189 -0.35518

H -6.31926 -1.55255 -1.21072

H -4.80381 -2.33025 -0.67974

H -6.22942 -2.31610 0.39445

C -3.91464 -0.17611 0.27947

H -3.69542 0.80421 0.71391

O -2.99799 -0.92566 -0.13457

PCM model: E =-2178.234707a.u., G =-2178.294959a.u.

Table S22 Structure 2···DMF(in DMF):

Pd 0.51887 0.73423 0.45745

I -0.41370 2.66704 -1.28235

C -1.24389 -0.30638 0.25962

C -1.42766 -1.25748 -0.73476

C -2.33074 -0.06289 1.08840

C -2.63260 -1.93985 -0.92592

C -3.56020 -0.71258 0.94660

C -3.69879 -1.65466 -0.07287

P 1.15749 -0.99260 1.85118

H 1.21360 -2.26298 1.25664

H 2.39998 -0.92951 2.50252

H 0.29109 -1.24027 2.93214

P 2.56642 1.96964 0.65550

H 3.34967 2.06168 -0.50889

H 2.44293 3.33493 0.97775

H 3.55116 1.58857 1.58728

F -0.40574 -1.54491 -1.56766

F -4.86374 -2.29256 -0.23182

F -2.21171 0.84464 2.07987

Cl -2.81546 -3.12015 -2.19295

Cl -4.89680 -0.36727 2.00797

N 5.71652 -1.92258 -0.09139

C 6.57864 -2.93291 -0.68807

H 7.00827 -3.57617 0.08759

H 6.00118 -3.55181 -1.37758

H 7.39852 -2.46134 -1.24117

C 6.32366 -1.00490 0.86292

H 5.55233 -0.33720 1.24346

H 6.76729 -1.56363 1.69396

H 7.11125 -0.41657 0.37927

C 4.41045 -1.82806 -0.41561

H 4.09794 -2.59318 -1.14589

O 3.61558 -0.99480 0.03422

PCM model: E =-2521.360771a.u., G =-2521.426465a.u.

Table S23 Structure A(in MeCN):

Pd -1.26873 -0.57922 0.04190

I -1.52048 2.15795 -0.18614

P -0.94442 -2.87693 0.19536

H 0.28933 -3.42089 -0.19742

H -1.08200 -3.43516 1.47973

H -1.84419 -3.67350 -0.53642

C 0.73313 -0.37150 0.03324

C 1.45272 -0.17579 1.20548

C 1.46471 -0.39894 -1.14749

C 2.84003 -0.00361 1.22594

C 2.85188 -0.23070 -1.18672

C 3.53127 -0.03209 0.01492

F 0.82193 -0.59439 -2.31639

F 4.85906 0.13018 0.00562

F 0.79969 -0.14944 2.38420

Cl 3.72308 -0.26570 -2.69257

Cl 3.69703 0.23970 2.72073

C -4.54007 -0.92592 0.09664

N -3.38889 -0.81649 0.07217

C -5.98892 -1.04902 0.12675

H -6.32824 -1.62851 -0.73535

H -6.29520 -1.55515 1.04554

H -6.44056 -0.05406 0.09435

PCM model: E =-2062.528213a.u., G =-2062.582846a.u.

Table S24 StructuretsA2(in MeCN):

Pd 1.08906 -0.06100 -0.50860

I 1.20447 -0.57983 2.20877

P 2.94365 -2.18448 -0.99496

H 2.43547 -3.48538 -0.75748

H 3.66205 -2.52193 -2.17256

H 4.04650 -2.28976 -0.11271

P 0.75328 0.42976 -2.73888

H 0.10278 1.63783 -3.05000

H 1.91278 0.53756 -3.52976

H -0.00870 -0.47773 -3.49637

C -0.91631 0.09561 -0.35229

C -1.52940 1.30775 -0.05498

C -1.75131 -1.00607 -0.50044

C -2.91173 1.43812 0.10575

C -3.13920 -0.93042 -0.35056

C -3.71006 0.30451 -0.04425

F -1.21883 -2.20654 -0.79742

F -5.03508 0.40361 0.10358

F -0.77530 2.41348 0.09162

Cl -4.14517 -2.33771 -0.54007

Cl -3.63554 2.97462 0.48524

C 4.21125 1.79588 -0.50923

N 3.24860 1.15125 -0.53852

C 5.42354 2.60323 -0.46857

H 5.84284 2.69333 -1.47376

H 6.16057 2.13099 0.18582

H 5.19215 3.60042 -0.08594

PCM model: E =-2405.633651a.u., G =-2405.697522a.u.

Table S25 StructureMeCN(in MeCN):

C 0.00000 0.00000 0.27848

N 0.00000 0.00000 1.43967

C 0.00000 0.00000 -1.18039

H 0.00000 1.02679 -1.55541

H 0.88923 -0.51340 -1.55541

H -0.88923 -0.51340 -1.55541

PCM model: E =-132.721417 a.u., G =-132.744375 a.u.

Table S26 Structure2···2(in MeCN):

Pd -3.76522 -1.22728 -1.00913

I -4.69575 -1.90396 1.49900

P -3.64817 -3.56970 -1.52261

H -4.84309 -4.30338 -1.40145

H -3.22203 -4.01203 -2.79255

H -2.80102 -4.33960 -0.70384

P -2.99201 -0.45322 -3.04506

H -3.87878 0.37057 -3.76046

H -1.84918 0.36345 -2.99198

H -2.61756 -1.37414 -4.04171

C -3.86783 0.76586 -0.50458

C -2.79263 1.43403 0.06427

C -5.03160 1.50354 -0.67748

C -2.84823 2.77151 0.46558

C -5.14815 2.84340 -0.29704

C -4.04189 3.46880 0.27863

F -6.10900 0.91340 -1.23391

F -4.12542 4.75024 0.65138

F -1.62728 0.77222 0.24119

Cl -6.63084 3.72542 -0.52811

Cl -1.47285 3.56561 1.17822

Pd 2.93995 -0.09634 1.38535

C 4.63444 0.23069 0.26258

C 4.72822 1.29644 -0.62221

C 5.72344 -0.62874 0.31429

C 5.84189 1.51374 -1.43849

C 6.86387 -0.46296 -0.47687

C 6.90936 0.61944 -1.35576

P 4.01327 1.19555 2.97467

H 4.34511 2.50310 2.57802

H 3.38537 1.44395 4.20990

H 5.26509 0.71967 3.40267

P 0.93412 -0.50775 2.63904

H 0.60786 -1.85727 2.86868

H 0.78031 0.00173 3.94558

H -0.26222 -0.05336 2.05528

I 1.87869 -1.60883 -0.66418

F 3.70464 2.17016 -0.71135

F 5.69423 -1.67812 1.16141

F 7.98810 0.80342 -2.12438

Cl 5.91156 2.86231 -2.53716

Cl 8.20368 -1.57029 -0.38042

PCM model: E =-4545.86909a.u., G =-4545.960459a.u.

Table S27 StructureB(in MeCN):

Pd -1.39302 -0.26893 -0.68566

I -2.51891 -2.69995 -0.01576

C -3.13479 0.60495 -0.14246

C -3.36656 1.01534 1.16452

C -4.16739 0.79869 -1.05176

C -4.57404 1.58648 1.57563

C -5.39420 1.36540 -0.69452

C -5.58617 1.75575 0.63072

P -0.72611 1.88610 -1.20539

H -0.85976 2.85856 -0.19890

H 0.59560 2.11133 -1.62937

H -1.44706 2.49635 -2.24837

F -2.39785 0.85887 2.08757

F -6.75010 2.30138 0.99804

F -3.99506 0.42739 -2.33527

Cl -4.82342 2.08016 3.22538

Cl -6.66199 1.58612 -1.86546

Pd 2.54064 -1.41201 0.79982

P 3.77724 -1.25003 2.73483

H 3.46753 -0.15042 3.55283

H 3.72987 -2.30742 3.66114

H 5.16264 -1.09164 2.56371

C 3.39586 0.41053 0.35978

C 2.76615 1.61593 0.63725

C 4.63397 0.49009 -0.26515

C 3.31956 2.85899 0.31737

C 5.23693 1.70198 -0.61321

C 4.56435 2.88656 -0.31259

P 1.58414 -3.56706 1.27265

H 0.17949 -3.64916 1.19642

H 1.95755 -4.59634 0.38796

H 1.82768 -4.20211 2.50742

F 1.55313 1.60462 1.23496

F 5.29852 -0.64792 -0.55242

F 5.11801 4.06042 -0.63038

Cl 2.49581 4.34495 0.69178

Cl 6.78851 1.75002 -1.39807

I 1.10162 -1.37758 -1.58883

PCM model: E =-4202.73459a.u., G =-4202.815461a.u.

Table S28Structurets B2(in MeCN):

Pd -1.59733 -0.69446 -0.85945

I -3.01672 -2.52136 0.65727

P -1.88298 -2.63539 -3.27621

H -1.73193 -3.99675 -2.90784

H -1.44142 -2.81561 -4.61661

H -3.26406 -2.73829 -3.58368

P -0.62740 0.95475 -2.15419

H -1.48898 1.76190 -2.91933

H 0.27984 0.51826 -3.13623

H 0.13737 1.93031 -1.49146

C -2.90272 0.73631 -0.29327

C -4.06611 1.02519 -0.99587

C -2.67226 1.46856 0.86602

C -4.98323 1.99224 -0.57362

C -3.55584 2.44597 1.33167

C -4.71535 2.69862 0.59869

F -1.55520 1.23809 1.58515

F -5.57605 3.62965 1.02229

F -4.33878 0.35513 -2.13138

Cl -3.23017 3.33685 2.79053

Cl -6.43149 2.31882 -1.48101

Pd 2.11701 -0.51191 1.57661

C 3.44707 0.49371 0.36355

C 4.69854 -0.04055 0.08374

C 3.14158 1.70097 -0.24786

C 5.61480 0.57263 -0.77473

C 4.01478 2.36242 -1.11596

C 5.25680 1.78158 -1.37269

P 2.98141 0.82137 3.24657

H 2.50270 0.66817 4.56098

H 4.36927 0.73228 3.44771

H 2.81764 2.20409 3.05521

P 0.62003 -1.75057 2.98657

H 1.04948 -3.05424 3.30177

H 0.31533 -1.27746 4.27930

H -0.67090 -2.01302 2.48518

I 1.20248 -1.97900 -0.60121

F 5.05832 -1.20637 0.65816

F 1.94409 2.28013 -0.00042

F 6.11415 2.39077 -2.19754

Cl 7.16828 -0.13970 -1.10150

Cl 3.58288 3.87386 -1.86216

PCM model: E =-4545.84632a.u., G =-4545.933655a.u.

Table S29 StructureA···PH3(in MeCN):

Pd -1.27651 -0.62293 -0.52415

I -1.53267 0.41058 2.01792

P -0.87313 -1.49872 -2.63929

H -0.16647 -2.71304 -2.69753

H -1.99633 -1.79752 -3.43290

H -0.11562 -0.70987 -3.52315

C 0.72881 -0.54695 -0.33440

C 1.45317 -1.60277 0.20658

C 1.45635 0.57442 -0.71501

C 2.83925 -1.56214 0.38132

C 2.84231 0.66984 -0.56323

C 3.52577 -0.41223 -0.00864

F 0.80862 1.62529 -1.25857

F 4.85205 -0.34811 0.14668

F 0.80375 -2.72034 0.58536

Cl 3.70940 2.09624 -1.05277

Cl 3.70216 -2.90797 1.06733

C -4.54117 -0.75414 -0.87138

N -3.39176 -0.70579 -0.75293

C -5.98812 -0.81015 -1.00932

H -6.29908 -0.21312 -1.87028

H -6.30378 -1.84614 -1.15597

H -6.45837 -0.41383 -0.10585

P 0.05230 5.38894 -0.25726

H 0.29346 3.99735 -0.41103

H -1.35045 5.23707 -0.08455

H 0.32758 5.39288 1.13713

PCM model: E =-2405.648633 a.u., G =-2405.716494 a.u.

Table S30 Structure2···MeCN(in MeCN):

Pd -1.04316 -0.43700 0.60067

I -0.89607 -2.10705 -1.59363

P -3.32185 -1.12628 0.89425

H -3.55046 -2.50767 1.04095

H -4.08532 -0.63757 1.97395

H -4.19731 -0.84359 -0.17015

P -1.00425 1.04311 2.37464

H -0.76574 2.38565 2.04064

H -2.13379 1.15636 3.20269

H 0.00922 0.81343 3.32271

C 0.90978 0.14201 0.30961

C 1.24405 1.20998 -0.51237

C 1.96770 -0.54039 0.89528

C 2.56399 1.59267 -0.76820

C 3.30706 -0.20464 0.67778

C 3.59297 0.87086 -0.16337

F 1.70747 -1.58138 1.71325

F 4.86546 1.21532 -0.38904

F 0.26091 1.92144 -1.10179

Cl 4.59969 -1.09532 1.43086

Cl 2.93234 2.93586 -1.81297

C -4.20849 2.99027 0.10228

N -3.56965 2.39326 0.86601

C -5.01285 3.74170 -0.85464

H -5.33211 3.08634 -1.66898

H -5.89710 4.15055 -0.35911

H -4.42550 4.56437 -1.27026

PCM model: E =-2405.654375a.u., G =-2405.71844a.u.

Table S31 StructurePH3 (in MeCN):

P 0.00000 0.00000 0.12635

H 0.00000 1.20134 -0.63178

H -1.04039 -0.60067 -0.63178

H 1.04039 -0.60067 -0.63178

PCM model: E =-343.122524a.u., G =-343.142525a.u.

Table S32 Structure2 (in MeCN):

Pd 1.40714 0.69881 -0.00063

I 1.83461 -2.02543 0.00105

P 3.79606 0.99656 0.00016

H 4.49298 0.42325 -1.07955

H 4.37253 2.28443 0.00022

H 4.49180 0.42371 1.08087

P 0.94700 2.96536 -0.00251

H -0.39610 3.37714 -0.00188

H 1.45858 3.70507 1.08035

H 1.45686 3.70289 -1.08766

C -0.61853 0.36910 -0.00045

C -1.33799 0.24512 1.17975

C -1.33839 0.24335 -1.18019

C -2.71202 -0.01040 1.21172

C -2.71245 -0.01220 -1.21129

C -3.39148 -0.13992 0.00043

F -0.69803 0.37482 -2.36084

F -4.70669 -0.38424 0.00086

F -0.69722 0.37830 2.35998

Cl -3.57116 -0.16765 -2.71793

Cl -3.57017 -0.16371 2.71890

PCM model: E =-2272.933214a.u., G =-2272.984441a.u.

Table S33 StructureB···PH3 (in MeCN):

Pd -1.27586 -0.28867 -0.49028

I -2.28108 -2.86224 -0.42907

C -3.01452 0.33758 0.33407

C -3.18526 0.39809 1.71164

C -4.10501 0.70041 -0.44660

C -4.38599 0.78996 2.30969

C -5.32892 1.09882 0.09812

C -5.45677 1.13886 1.48652

P -0.69851 1.95192 -0.46088

H -0.84846 2.63675 0.75778

H 0.60918 2.31929 -0.82497

H -1.45792 2.76886 -1.32059

F -2.15998 0.06302 2.51911

F -6.61616 1.51784 2.03378

F -3.99671 0.66310 -1.79103

Cl -4.55675 0.84637 4.04036

Cl -6.67216 1.53567 -0.91759

Pd 2.76941 -1.57128 0.45511

P 4.15396 -1.84412 2.27557

H 3.87499 -1.01143 3.37241

H 4.22230 -3.10507 2.89507

H 5.51357 -1.56984 2.05238

C 3.51789 0.34972 0.44224

C 2.88010 1.40312 1.08243

C 4.68682 0.65946 -0.24139

C 3.36013 2.71588 1.05907

C 5.21407 1.95220 -0.30505

C 4.53674 2.97714 0.35594

P 1.92348 -3.82077 0.42640

H 0.52206 -3.94964 0.35453

H 2.31776 -4.59944 -0.67822

H 2.22588 -4.71159 1.47630

F 1.73115 1.16729 1.75522

F 5.35751 -0.32448 -0.87480

F 5.01998 4.22227 0.31577

Cl 2.52852 4.00299 1.88286

Cl 6.67987 2.29150 -1.17806

I 1.18103 -1.01941 -1.76578

P -3.28250 3.24452 -3.87831

H -4.68321 3.04190 -3.99718

H -2.94207 2.03809 -4.54639

H -3.18987 4.04428 -5.04992

PCM model: E =-4545.855187a.u., G =-4545.946182a.u.

Table S34 Structurets B2 (in PhCl):

Pd -1.60810 -0.72386 -0.84482

I -3.02856 -2.47310 0.73348

P -1.89945 -2.84974 -3.13014

H -1.67803 -4.15898 -2.63348

H -1.53997 -3.16033 -4.47254

H -3.29288 -3.02015 -3.33007

P -0.62527 0.86121 -2.21312

H -1.47539 1.69816 -2.96104

H 0.22532 0.37853 -3.22494

H 0.20730 1.81597 -1.60183

C -2.91382 0.72145 -0.32628

C -4.07094 0.99352 -1.04579

C -2.68963 1.48246 0.81518

C -4.98845 1.97389 -0.65555

C -3.57379 2.47397 1.24841

C -4.72784 2.70938 0.50077

F -1.57674 1.26883 1.54773

F -5.58839 3.65356 0.89315

F -4.33368 0.29677 -2.16644

Cl -3.25595 3.40283 2.68518

Cl -6.42745 2.28185 -1.58268

Pd 2.08019 -0.40921 1.58232

C 3.46653 0.50100 0.35401

C 4.71488 -0.06962 0.13800

C 3.19980 1.67802 -0.33036

C 5.66373 0.47872 -0.72934

C 4.10642 2.27447 -1.21116

C 5.34311 1.65792 -1.40374

P 2.93220 0.99493 3.19991

H 2.39767 0.95837 4.50263

H 4.30528 0.86401 3.47237

H 2.84314 2.36881 2.91511

P 0.51006 -1.53847 3.00380

H 0.93316 -2.80520 3.45201

H 0.14281 -0.96084 4.23749

H -0.75396 -1.85504 2.46446

I 1.21288 -1.97165 -0.53095

F 5.03965 -1.20432 0.78874

F 2.00830 2.29302 -0.14498

F 6.23146 2.20516 -2.23775

Cl 7.21108 -0.27628 -0.97271

Cl 3.72128 3.74940 -2.04947

PCM model: E =-4545.838431a.u., G =-4545.924601a.u.

Table S35 Structure2···2 (in PhCl):

Pd -2.41925 -0.95357 -1.06837

I -4.14637 -2.00218 0.79728

P -2.11947 -3.17849 -1.91392

H -3.28419 -3.80103 -2.40352

H -1.24194 -3.43220 -2.98924

H -1.67833 -4.15783 -1.00646

P -0.99694 0.09741 -2.56156

H -1.58707 1.10223 -3.35109

H 0.09127 0.79039 -2.00601

H -0.35183 -0.66856 -3.55088

C -2.76953 0.93580 -0.32667

C -2.08482 1.46183 0.75962

C -3.76870 1.73392 -0.86962

C -2.36534 2.71756 1.30524

C -4.09544 2.99722 -0.36900

C -3.38164 3.47949 0.72829

F -4.46600 1.27993 -1.93109

F -3.67068 4.68437 1.22918

F -1.09562 0.73786 1.33381

Cl -5.35740 3.95767 -1.08362

Cl -1.48422 3.33473 2.67455

Pd 1.96444 -0.75071 1.30757

C 3.38990 0.35744 0.31782

C 3.05798 1.40341 -0.53113

C 4.74211 0.05956 0.43054

C 4.00384 2.12526 -1.26418

C 5.73489 0.74572 -0.27452

C 5.34885 1.78129 -1.12668

P 2.14537 0.86331 2.94957

H 1.83274 2.17314 2.54560

H 1.37130 0.76116 4.12191

H 3.42665 1.05186 3.49856

P 0.31222 -2.10686 2.40256

H 0.69453 -3.42915 2.69840

H -0.21295 -1.72608 3.65603

H -0.88714 -2.33284 1.70127

I 1.89203 -2.51663 -0.80068

F 1.75846 1.75725 -0.66574

F 5.12961 -0.93488 1.25378

F 6.27687 2.45434 -1.81325

Cl 3.53395 3.42378 -2.32282

Cl 7.41613 0.33270 -0.10494

PCM model: E =-4545.863566a.u., G =-4545.950073a.u.

Table S36 Structure2 (in PhCl):

Pd 1.42031 0.70857 0.00074

I 1.83241 -2.00357 -0.00267

P 3.80482 0.96987 0.00151

H 4.49971 0.39261 -1.07767

H 4.39626 2.25287 0.00319

H 4.49925 0.38997 1.07956

P 0.85257 2.95155 0.00361

H 0.06762 3.39105 -1.07786

H 0.06904 3.38814 1.08729

H 1.86219 3.93524 0.00427

C -0.61198 0.38807 0.00039

C -1.32848 0.25041 1.18171

C -1.32879 0.25374 -1.18110

C -2.69893 -0.02336 1.21247

C -2.69925 -0.01994 -1.21228

C -3.37567 -0.15998 -0.00001

F -0.68874 0.39363 -2.35944

F -4.68672 -0.42025 -0.00018

F -0.68810 0.38696 2.36025

Cl -3.55554 -0.18300 -2.71822

Cl -3.55483 -0.19069 2.71818

PCM model: E =-2272.92787a.u., G =-2272.979317a.u.

Table S37 StructureB (in PhCl):

Pd 2.49952 -1.43388 0.68064

C 3.06914 0.52196 0.39025

C 2.24708 1.59288 0.71563

C 4.28395 0.82737 -0.20954

C 2.59206 2.92176 0.45016

F 1.05945 1.35529 1.30538

C 4.68280 2.13553 -0.49750

F 5.12501 -0.17447 -0.53703

C 3.82017 3.17947 -0.16063

Cl 1.52892 4.23425 0.86570

Cl 6.21211 2.47038 -1.25466

F 4.17528 4.44020 -0.42357

I 1.26374 -1.40153 -1.79751

P 1.94241 -3.76086 0.98291

P 3.54332 -1.18219 2.72231

H 3.04039 -4.64639 0.91032

H 1.39180 -4.17528 2.21110

H 1.06058 -4.37549 0.08015

H 3.60968 -2.27451 3.60929

H 4.89128 -0.78489 2.68771

H 2.98809 -0.19611 3.55582

I -1.68470 -2.33690 0.99480

P -1.16083 1.40131 -2.37180

H -2.31163 1.64936 -3.14329

H -0.96545 2.67551 -1.80442

H -0.17010 1.41274 -3.37245

C -3.02656 0.42903 -0.30872

C -3.11865 1.34713 0.73047

C -4.21501 0.05647 -0.92474

C -4.33746 1.88008 1.16093

C -5.45953 0.55815 -0.53316

C -5.50701 1.47331 0.51872

F -4.18171 -0.82208 -1.94459

F -1.99894 1.74948 1.35843

F -6.68434 1.97041 0.91073

Cl -4.40885 3.02629 2.46793

Cl -6.92431 0.06287 -1.33048

Pd -1.25323 -0.36448 -0.87481

PCM model: E =-4202.724853 a.u., G =-4202.805127 a.u.

Table S38 StructureA (in PhCl):

Pd -0.62203 0.18100 -0.08323

I 0.12712 2.79641 -0.00620

P -1.07897 -2.09861 -0.24486

H -0.38777 -2.80790 -1.24358

H -0.79126 -2.89626 0.87873

H -2.40672 -2.48730 -0.51307

C 1.30632 -0.35504 -0.01972

C 1.96307 -0.51539 1.19465

C 2.04820 -0.55468 -1.17761

C 3.31696 -0.85299 1.27464

C 3.40387 -0.89433 -1.14959

C 4.02950 -1.03784 0.08923

F 1.45065 -0.42444 -2.37515

F 5.32360 -1.36362 0.14143

F 1.28337 -0.34293 2.34154

Cl 4.29942 -1.13783 -2.61895

Cl 4.10610 -1.04171 2.81137

Cl -3.11337 1.04825 -0.08756

C -4.31716 -0.25904 0.02373

C -4.69039 -0.71878 1.28432

C -4.86127 -0.76976 -1.15226

C -5.64869 -1.73269 1.36144

H -4.25049 -0.29469 2.18000

C -5.81804 -1.78357 -1.05267

H -4.55172 -0.38468 -2.11747

C -6.21106 -2.26415 0.19851

H -5.95416 -2.10182 2.33543

H -6.25461 -2.19284 -1.95826

H -6.95568 -3.05077 0.26729

PCM model: E =-2621.541248 a.u., G =-2621.602497 a.u.

Table S39 StructurePhCl (in PhCl):

C 0.50030 0.00001 -0.00001

C -0.17871 -1.21753 -0.00002

C -1.57506 -1.20811 0.00002

C -2.27500 -0.00001 0.00000

C -1.57508 1.20810 -0.00001

C -0.17872 1.21753 0.00001

H 0.37257 -2.15115 -0.00001

H -2.11246 -2.15147 0.00002

H -3.36032 -0.00002 0.00001

H -2.11247 2.15146 -0.00001

H 0.37252 2.15117 0.00002

Cl 2.26669 0.00000 0.00000

PCM model: E =-691.764208 a.u., G =-691.794 a.u.

Table S40 Structurets A2 (in PhCl):

Pd -0.42247 -0.50335 0.17728

I 0.28348 -2.11397 -1.88996

P -1.66342 -3.05425 1.98178

H -0.51819 -3.76540 2.42340

H -2.05336 -4.02562 1.02520

H -2.51630 -3.54243 3.01005

P -0.94818 0.91751 1.94575

H -0.34608 0.63083 3.18533

H -0.64012 2.28593 1.82774

H -2.30466 0.98446 2.32136

C 1.40675 0.29224 0.22104

C 1.71033 1.44251 -0.49764

C 2.42999 -0.29185 0.95874

C 2.98877 2.00781 -0.49687

C 3.72351 0.23728 0.99000

C 3.99090 1.39134 0.25297

F 2.18162 -1.40190 1.67380

F 5.21873 1.91619 0.27067

F 0.74995 2.04639 -1.21859

Cl 4.97886 -0.51731 1.92515

Cl 3.33375 3.44894 -1.40468

C -4.61261 3.19113 -0.36122

C -5.60071 3.08422 0.62043

C -5.90262 1.83763 1.17286

C -5.22146 0.69277 0.75120

C -4.23982 0.82386 -0.23015

C -3.92179 2.05770 -0.79682

H -4.37630 4.15711 -0.79675

H -6.13502 3.96899 0.95185

H -6.67185 1.74816 1.93377

H -5.45299 -0.28035 1.16988

H -3.15845 2.12925 -1.56373

Cl -3.37751 -0.61934 -0.78098

PCM model: E =-2964.657599a.u., G =-2964.725777a.u.

Table S41 Structure2···PhCl (in PhCl):

Pd 0.10562 -0.95081 0.64066

I 0.94298 -2.50584 -1.45967

P -1.68544 -2.51498 0.96913

H -1.30900 -3.84050 1.25748

H -2.64515 -2.31782 1.98672

H -2.54265 -2.73514 -0.12436

P -0.39960 0.47594 2.39075

H 0.58999 0.59952 3.38329

H -0.59971 1.82698 2.05539

H -1.53597 0.23680 3.18884

C 1.68125 0.32721 0.30462

C 1.57592 1.39933 -0.57122

C 2.91847 0.13116 0.90300

C 2.64663 2.24891 -0.86452

C 4.02397 0.94815 0.64936

C 3.87336 2.00864 -0.24464

F 3.07586 -0.88938 1.77019

F 4.91345 2.80709 -0.50465

F 0.39531 1.64359 -1.17337

Cl 5.55684 0.66420 1.42266

Cl 2.47062 3.57905 -1.97253

C -7.11242 2.05008 0.88408

C -7.91448 1.36400 -0.03045

C -7.32430 0.54798 -0.99814

C -5.93549 0.41155 -1.05796

C -5.15400 1.10477 -0.13457

C -5.72185 1.92548 0.83890

H -7.56480 2.68777 1.63750

H -8.99443 1.46586 0.00989

H -7.94198 0.01331 -1.71333

H -5.46873 -0.21796 -1.80748

H -5.09180 2.45697 1.54358

Cl -3.39572 0.93918 -0.20449

PCM model: E =-2964.683929a.u., G =-2964.753869a.u.

Table S42 StructureA···PH3 (in PhCl):

Pd -0.48270 -0.21318 0.19995

I 0.26346 0.21505 2.78605

P -0.93416 -0.55690 -2.06179

H -0.41397 0.38927 -2.96366

H -0.45068 -1.74801 -2.63447

H -2.28341 -0.59480 -2.46653

C 1.44848 -0.21219 -0.33202

C 2.19205 -1.38643 -0.32439

C 2.10764 0.95760 -0.69013

C 3.54992 -1.41609 -0.65404

C 3.46385 0.97936 -1.02805

C 4.17694 -0.21960 -1.00353

F 1.42920 2.11841 -0.71786

F 5.47317 -0.22298 -1.32490

F 1.59450 -2.54316 0.01103

Cl 4.25514 2.46183 -1.47144

Cl 4.44734 -2.90405 -0.63300

Cl -2.97834 -0.21091 1.07610

C -4.18747 -0.63759 -0.16014

C -4.56105 -1.97261 -0.29369

C -4.73554 0.37743 -0.94070

C -5.52460 -2.29668 -1.25212

H -4.11724 -2.73666 0.33470

C -5.69743 0.03097 -1.89363

H -4.41979 1.40689 -0.81077

C -6.09142 -1.29988 -2.04988

H -5.83026 -3.33161 -1.36942

H -6.13668 0.80812 -2.51120

H -6.83992 -1.55990 -2.79162

P -2.17312 4.00651 -0.68691

H -0.75903 3.91420 -0.59124

H -2.35924 4.23679 0.70243

H -2.17019 5.38720 -1.02465

PCM model: E =-2964.661535 a.u., G =-2964.73302 a.u.

Table S43 StructureB···PH3 (in PhCl):

Pd -2.62640 -1.25388 -0.99776

C -3.24694 0.56200 -0.25405

C -2.47530 1.71202 -0.35781

C -4.44287 0.67506 0.44325

C -2.84966 2.93126 0.21540

F -1.30839 1.66336 -1.02904

C -4.87004 1.86713 1.03479

F -5.23709 -0.40798 0.56457

C -4.05679 2.99439 0.91296

Cl -1.84655 4.34517 0.07273

Cl -6.37334 1.95934 1.90405

F -4.43894 4.14748 1.46855

I -1.21649 -1.69208 1.34462

P -2.00252 -3.42733 -1.83969

P -3.81830 -0.62551 -2.86910

H -3.06257 -4.35643 -1.92481

H -1.49845 -3.52997 -3.15065

H -1.05478 -4.18601 -1.13487

H -3.89008 -1.49889 -3.97146

H -5.17917 -0.33668 -2.66880

H -3.37509 0.55359 -3.49222

I 1.64718 -1.94838 -1.68803

P 1.01593 1.07988 2.32236

H 2.17966 1.70903 2.80172

H 0.19255 2.20463 2.11808

H 0.47439 0.58324 3.52304

C 2.90571 0.62204 0.04261

C 2.90534 1.68805 -0.84855

C 4.13334 0.25168 0.57678

C 4.07209 2.36406 -1.21795

C 5.32935 0.89273 0.24061

C 5.28481 1.95217 -0.66562

F 4.19263 -0.76479 1.45941

F 1.74285 2.10040 -1.38642

F 6.41432 2.58324 -1.00224

Cl 4.02720 3.69270 -2.34057

Cl 6.84681 0.39275 0.92919

Pd 1.20729 -0.36392 0.51894

P 3.10731 -2.70507 4.09721

H 2.30771 -3.19877 3.03203

H 2.94898 -3.87287 4.89390

H 4.33062 -3.13779 3.51906

PCM model: E =-4545.845695a.u., G =-4545.938865a.u.

Table S44 StructurePH3 (in PhCl):

P 0.00000 0.00000 0.12683

H 0.00000 1.20023 -0.63416

H -1.03943 -0.60012 -0.63416

H 1.03943 -0.60012 -0.63416

PCM model: E =-343.122161a.u., G =-343.142163a.u.

Table S45 Structure2 (in THF):

Pd 1.41925 0.70795 0.00029

C -0.61321 0.38656 -0.00001

C -1.33006 0.25059 1.18129

C -1.33071 0.25140 -1.18099

C -2.70072 -0.02204 1.21267

F -0.68963 0.38684 2.36006

C -2.70140 -0.02117 -1.21178

F -0.69090 0.38841 -2.36001

C -3.37791 -0.15907 0.00059

Cl -3.55651 -0.18781 2.71885

Cl -3.55806 -0.18584 -2.71758

F -4.68930 -0.41859 0.00087

I 1.83799 -2.00673 -0.00146

P 3.80158 0.98432 0.00241

P 0.85272 2.95011 -0.00113

H 4.50123 0.41202 -1.07633

H 4.38076 2.27236 0.00421

H 4.49916 0.40984 1.08132

H 1.86661 3.92872 -0.00218

H 0.06953 3.38708 -1.08460

H 0.06992 3.38900 1.08185

PCM model: E =-2272.92926a.u., G =-2272.980618a.u.

Table S46 Structure ts B2 (in THF):

Pd 2.08613 -0.41077 1.58404

C 3.46980 0.49966 0.35311

C 3.20182 1.67760 -0.32930

C 4.71753 -0.07075 0.13325

C 4.10680 2.27533 -1.21089

F 2.01070 2.29236 -0.14130

C 5.66463 0.47873 -0.73522

F 5.04364 -1.20713 0.78078

C 5.34304 1.65912 -1.40686

Cl 3.72027 3.75170 -2.04628

Cl 7.21139 -0.27653 -0.98348

F 6.22992 2.20756 -2.24198

I 1.20996 -1.97172 -0.53019

P 0.51885 -1.53609 3.01179

P 2.94473 0.98990 3.20146

H 0.93974 -2.80373 3.45929

H 0.15553 -0.95673 4.24550

H -0.74701 -1.85043 2.47611

H 2.41301 0.95037 4.50489

H 4.31834 0.85547 3.46841

H 2.85602 2.36393 2.91807

H -1.52676 -3.13977 -4.48120

P -1.89676 -2.84559 -3.13826

Pd -1.61187 -0.72374 -0.84488

H -3.28808 -3.02053 -3.34974

H -1.67291 -4.15940 -2.65444

C -2.91625 0.72302 -0.32661

I -3.03329 -2.47700 0.73414

P -0.62796 0.86320 -2.20912

C -2.68998 1.48579 0.81336

C -4.07488 0.99408 -1.04402

H 0.22255 0.37977 -3.22038

H 0.20492 1.81476 -1.59370

H -1.47744 1.70176 -2.95544

C -3.57361 2.47757 1.24713

F -1.57590 1.27329 1.54413

C -4.99189 1.97463 -0.65321

F -4.34046 0.29537 -2.16301

C -4.72911 2.71179 0.50146

Cl -3.25332 3.40810 2.68225

Cl -6.43327 2.28058 -1.57761

F -5.58941 3.65608 0.89451

PCM model: E =-4545.840343a.u., G =-4545.926858a.u.

Table S47 StructureA (in THF):

Pd 0.94541 0.50192 0.29572

C -1.04681 0.32330 0.17801

C -1.79086 -0.30326 1.17056

C -1.74840 0.79798 -0.92432

C -3.17641 -0.46839 1.08713

F -1.16294 -0.77692 2.26322

C -3.13259 0.65968 -1.05810

F -1.07787 1.41968 -1.91320

C -3.83861 0.01849 -0.04010

Cl -4.06752 -1.26169 2.35258

Cl -3.96855 1.26861 -2.45652

F -5.16341 -0.12559 -0.14336

I 1.21545 -1.92836 -0.93300

P 0.57997 2.54557 1.34030

H 1.72238 3.25846 1.75438

H -0.10012 3.53999 0.61189

H -0.17699 2.54870 2.52720

C 3.95980 -0.04999 1.28588

C 5.33564 0.98318 -0.39627

C 5.29041 -0.22993 0.54842

H 3.43168 -0.98973 1.45798

H 4.07151 0.48664 2.23328

H 5.98380 0.82543 -1.26161

H 5.67783 1.87783 0.13431

H 5.28078 -1.15896 -0.02957

H 6.13599 -0.26636 1.23926

O 3.13816 0.78934 0.41454

C 3.87200 1.12810 -0.79541

H 3.57595 2.14009 -1.08082

H 3.59075 0.42746 -1.58888

PCM model: E =-2162.146666a.u., G =-2162.205338a.u.

Table S48 StructureB···PH3 (in THF):

Pd 2.58943 -1.55710 0.69135

C 3.42175 0.28281 0.29246

C 2.75109 1.47222 0.54740

C 4.66668 0.38819 -0.31432

C 3.27337 2.72486 0.21150

F 1.53930 1.43319 1.13454

C 5.23960 1.61206 -0.67138

F 5.36628 -0.73493 -0.57834

C 4.52598 2.77997 -0.40127

Cl 2.39680 4.19052 0.54243

Cl 6.80160 1.69420 -1.43223

F 5.04860 3.96461 -0.73097

I 1.17720 -1.39835 -1.68740

P 1.70621 -3.76214 1.11089

P 3.81466 -1.42282 2.63968

H 2.60794 -4.82287 0.87576

H 1.29136 -4.09524 2.41525

H 0.59906 -4.19944 0.36669

H 3.80691 -2.50342 3.54271

H 5.19567 -1.20815 2.49144

H 3.46074 -0.36178 3.49085

I -1.52491 -1.59291 1.49672

P -1.09196 1.42934 -2.54349

H -2.27847 1.63030 -3.27321

H -0.77576 2.76015 -2.20970

H -0.17726 1.20137 -3.58950

C -2.87391 0.93139 -0.25316

C -2.86770 2.01638 0.61511

C -4.11104 0.52506 -0.73798

C -4.03593 2.67542 1.00946

C -5.30889 1.14777 -0.37657

C -5.25698 2.22663 0.50624

F -4.17446 -0.51029 -1.60018

F -1.69773 2.46403 1.10577

F -6.38794 2.84079 0.86755

Cl -3.98310 4.02679 2.10378

Cl -6.83674 0.60454 -1.00658

Pd -1.17726 -0.04742 -0.76167

H -6.45692 -4.29516 -1.34002

P -5.08086 -4.32167 -0.98123

H -4.91038 -2.91747 -1.10828

H -5.34083 -4.27032 0.41517

PCM model: E =-4545.847215a.u., G =-4545.939326a.u.

Table S49 StructureB (in THF):

Pd 2.74151 -1.38924 0.67560

C 3.10734 0.61466 0.37425

C 2.20419 1.59071 0.77390

C 4.23828 1.05134 -0.30240

C 2.38851 2.95058 0.50651

F 1.09068 1.22350 1.43884

C 4.47837 2.39690 -0.59523

F 5.15390 0.14575 -0.70203

C 3.53772 3.34135 -0.18270

Cl 1.22422 4.14035 1.01197

Cl 5.90761 2.89747 -1.45022

F 3.73946 4.63479 -0.44948

I 1.26637 -1.48959 -1.67709

P 2.27516 -3.72974 0.96441

P 4.00839 -1.10155 2.57434

H 2.72156 -4.58616 -0.05980

H 2.75073 -4.42952 2.09308

H 0.90492 -4.05072 1.00749

H 4.26056 -2.21054 3.40352

H 5.31057 -0.61483 2.36733

H 3.51039 -0.17295 3.50444

I -1.94497 -2.60785 0.71862

P -0.95446 1.52351 -2.02979

H -2.01712 1.88047 -2.88083

H -0.80411 2.72007 -1.30277

H 0.13401 1.62195 -2.91778

C -3.00771 0.41483 -0.24518

C -3.14544 1.14678 0.92814

C -4.15059 0.24733 -1.01754

C -4.36552 1.69127 1.33955

C -5.39461 0.76969 -0.65229

C -5.48911 1.49225 0.53717

F -4.07128 -0.44407 -2.17076

F -2.07129 1.34595 1.71309

F -6.66668 2.00455 0.90853

Cl -4.49472 2.59904 2.81828

Cl -6.80109 0.53358 -1.64863

Pd -1.24012 -0.40890 -0.78240

PCM model: E =-4202.727559a.u., G =-4202.808075a.u.

Table S50 StructureTHF (in THF):

C 1.18508 -0.46084 0.00000

O 0.00001 -1.26087 0.00000

C -1.18507 -0.46086 0.00000

C -0.77365 1.02646 0.00000

C 0.77363 1.02647 0.00000

H 1.78245 -0.71603 0.88527

H 1.78245 -0.71603 -0.88527

H -1.78244 -0.71607 -0.88527

H -1.78244 -0.71607 0.88526

H -1.16978 1.54092 -0.87917

H -1.16978 1.54092 0.87917

H 1.16975 1.54094 -0.87917

H 1.16975 1.54094 0.87917

PCM model: E =-232.341074a.u., G =-232.367751a.u.

Table S51 Structure2···THF (in THF):

Pd 0.70237 -0.75704 0.53441

C -1.10924 0.18798 0.29426

C -2.23806 -0.20234 1.00236

C -1.27723 1.22572 -0.61262

C -3.49214 0.38904 0.82510

F -2.13566 -1.19728 1.90706

C -2.50533 1.85612 -0.83302

F -0.21513 1.65887 -1.32497

C -3.61295 1.42294 -0.10393

Cl -4.87987 -0.13829 1.73402

Cl -2.66604 3.15265 -1.98352

F -4.80023 2.00839 -0.29271

I 0.02660 -2.57520 -1.41631

P 2.82292 -1.85588 0.74357

P 1.11148 0.85516 2.13845

H 3.67277 -1.76795 -0.37311

H 3.72434 -1.50423 1.76825

H 2.79481 -3.25336 0.91875

H 2.27056 0.77913 2.93081

H 1.17570 2.18116 1.67970

H 0.12219 0.97240 3.13335

H 3.47528 0.84159 -1.60644

C 3.42433 1.68358 -0.90712

O 3.68298 1.20344 0.43536

C 4.48325 2.75883 -1.20290

H 2.40529 2.08423 -0.93090

C 4.84798 1.86327 0.96193

C 4.93859 3.18491 0.20240

H 4.07986 3.58405 -1.79497

H 5.32381 2.32767 -1.75665

H 4.71239 1.97725 2.04165

H 5.74154 1.24564 0.78695

H 4.24378 3.91585 0.63038

H 5.94336 3.61519 0.21923

PCM model: E =-2505.277019a.u., G =-2505.340651a.u.

Table S52 Structurets A2 (in THF):

Pd -0.80678 -0.31195 -0.53653

C 1.16521 0.02215 -0.33472

C 2.09020 -1.01566 -0.33320

C 1.66407 1.30858 -0.16301

C 3.46083 -0.80439 -0.15612

F 1.66749 -2.28125 -0.50996

C 3.02433 1.57348 0.01835

F 0.81527 2.35319 -0.17025

C 3.91694 0.50148 0.02240

Cl 4.58496 -2.13187 -0.15907

Cl 3.60609 3.19857 0.23474

F 5.22298 0.72870 0.19175

I -1.01181 -0.46502 2.19561

P -2.34987 -2.78810 -0.80280

P -0.44321 -0.10533 -2.81318

H -3.31361 -3.12193 0.18078

H -1.45873 -3.84414 -0.49263

H -2.99865 -3.46473 -1.87188

H -1.58434 -0.15509 -3.63808

H 0.36838 -1.07585 -3.42999

H 0.17159 1.06829 -3.28970

H -2.27302 2.48465 -0.44223

C -3.09272 2.07936 -1.04648

O -3.13677 0.63999 -0.86426

C -4.45198 2.60307 -0.58090

H -2.88496 2.28356 -2.10169

C -4.29964 0.27962 -0.07494

C -4.82653 1.58904 0.51037

H -5.17855 2.57038 -1.40000

H -4.39469 3.63162 -0.21575

H -5.03705 -0.19194 -0.73766

H -3.98748 -0.43984 0.68478

H -5.89940 1.54979 0.71564

H -4.30503 1.82234 1.44463

PCM model: E =-2505.254198a.u., G =-2505.317983a.u.

Table S53 StructureA…PH3 (in THF):

Pd -1.00777 0.06123 0.45674

C 0.96943 -0.21810 0.29242

C 1.77157 0.62491 -0.46741

C 1.60578 -1.28053 0.92488

C 3.14788 0.43244 -0.61725

F 1.21125 1.68107 -1.09278

C 2.97790 -1.51914 0.81000

F 0.88105 -2.12233 1.68597

C 3.74175 -0.65180 0.02868

Cl 4.11096 1.51061 -1.58430

Cl 3.73026 -2.86213 1.61937

F 5.05643 -0.85779 -0.09651

I -1.41292 -1.57136 -1.70479

P -0.53166 1.45699 2.25189

H -1.63746 1.96017 2.96503

H 0.25092 0.94295 3.30256

H 0.16751 2.64501 1.96112

C -3.87678 1.32222 -0.19402

C -5.44757 -0.05811 0.99575

C -5.29608 0.75522 -0.30097

H -3.34602 1.34277 -1.14798

H -3.85359 2.31972 0.25606

H -6.20849 -0.83889 0.92288

H -5.70014 0.59443 1.83795

H -5.37712 0.09715 -1.17139

H -6.04317 1.54612 -0.40064

O -3.16552 0.42697 0.71695

C -4.04881 -0.63708 1.17067

H -3.77589 -0.86524 2.20346

H -3.88966 -1.52187 0.54529

H 2.52724 4.65176 -0.58001

P 1.23808 4.88245 -0.03101

H 1.36963 6.29810 -0.03538

H 0.57626 4.83296 -1.28678

PCM model: E =-2505.267333a.u., G =-2505.33441a.u.

Table S54 Structure2···2 (in THF):

Pd 1.98226 -0.73247 1.32421

C 3.40788 0.35835 0.31550

C 3.07549 1.40093 -0.53754

C 4.75897 0.05205 0.41759

C 4.01958 2.11138 -1.28392

F 1.77736 1.76250 -0.66357

C 5.74996 0.72656 -0.30108

F 5.14751 -0.94041 1.24304

C 5.36336 1.75923 -1.15635

Cl 3.54896 3.40594 -2.34731

Cl 7.42999 0.30246 -0.14474

F 6.28977 2.42116 -1.85619

I 1.88765 -2.51842 -0.76873

P 0.32634 -2.06469 2.44200

P 2.19023 0.88800 2.95705

H 0.70321 -3.38362 2.75889

H -0.19651 -1.66078 3.68889

H -0.87315 -2.29814 1.74388

H 1.42446 0.79625 4.13543

H 3.47796 1.06547 3.49401

H 1.88703 2.19892 2.54964

H -1.69949 -4.16326 -1.00412

P -2.12430 -3.18062 -1.91589

Pd -2.42874 -0.95625 -1.06935

H -3.28390 -3.79823 -2.42336

H -1.23225 -3.43383 -2.97896

C -2.77934 0.93405 -0.32993

I -4.18417 -2.00176 0.77538

P -0.98863 0.09028 -2.54755

C -2.08752 1.46312 0.75033

C -3.78431 1.72921 -0.86639

H -0.33065 -0.68074 -3.52402

H -1.57030 1.09030 -3.34912

H 0.09118 0.78734 -1.98082

C -2.36705 2.71868 1.29705

F -1.09187 0.74228 1.31699

C -4.11025 2.99217 -0.36453

F -4.48935 1.27231 -1.92162

C -3.38941 3.47741 0.72681

Cl -1.47731 3.33916 2.65918

Cl -5.38054 3.94876 -1.07019

F -3.67800 4.68219 1.22873

PCM model: E =-4545.865505a.u., G =-4545.952112a.u.

Table S55 StructurePH3 (in THF):

P 0.00000 0.00000 0.12671

H 0.00000 1.20052 -0.63354

H -1.03968 -0.60026 -0.63354

H 1.03968 -0.60026 -0.63354

PCM model: E =-343.122254a.u., G =-343.142255a.u.

B)Gasphase

Table S56 Structure2+DMF (in gas phase):

Pd -0.67599 -0.96165 0.56564

I -0.41402 -1.99806 -1.93002

C 1.10993 0.02282 0.32368

C 1.19564 1.22560 -0.36334

C 2.30009 -0.49950 0.81360

C 2.40178 1.89753 -0.57752

C 3.53770 0.12444 0.62811

C 3.57446 1.32843 -0.07731

P -0.73209 0.02045 2.66670

H -0.66963 1.42310 2.72887

H -1.78805 -0.22503 3.56562

H 0.36893 -0.30109 3.49062

P -2.77073 -2.10977 0.68848

H -3.74349 -1.70619 -0.24534

H -2.77490 -3.49686 0.43955

H -3.56636 -2.08735 1.85864

F 0.06831 1.78971 -0.85301

F 4.74123 1.94948 -0.26484

F 2.27173 -1.65197 1.51060

Cl 2.45795 3.40644 -1.44044

Cl 5.00208 -0.56510 1.26075

N -4.02431 2.63647 -0.01027

C -3.72125 3.49341 -1.14571

H -3.96704 4.53802 -0.92031

H -2.65751 3.42677 -1.38426

H -4.29474 3.18601 -2.02809

C -5.40267 2.57923 0.45218

H -5.44589 1.91525 1.31506

H -5.75103 3.57794 0.73973

H -6.05946 2.19686 -0.33821

C -3.06376 1.89474 0.58803

H -2.06933 2.03563 0.13665

O -3.24671 1.13084 1.54085

Gas phase: E =-2521.339644a.u., G =-2521.404843a.u.

Table S57 StructureA(DMF) (in gas phase):

Pd 0.85482 0.57510 -0.00576

I 1.06300 -2.11399 -0.13436

C -1.13831 0.35359 0.01304

C -1.84311 0.22586 1.20451

C -1.87473 0.31655 -1.16568

C -3.23032 0.05595 1.24388

C -3.26275 0.14919 -1.18085

C -3.93093 0.01428 0.03731

P 0.46761 2.86594 0.11467

H -0.25100 3.36207 1.22277

H 1.57265 3.74694 0.14373

H -0.28163 3.47191 -0.91598

F -1.23899 0.45805 -2.34132

F -1.17683 0.27934 2.37114

F -5.25674 -0.14206 0.04923

Cl -4.07488 -0.09487 2.75503

Cl -4.14748 0.11359 -2.67589

N 5.23367 0.37446 0.08712

C 6.21588 -0.67586 0.32253

H 5.70665 -1.61450 0.54815

H 6.84105 -0.81988 -0.56561

H 6.86325 -0.41309 1.16653

C 5.73379 1.70268 -0.24610

H 6.34851 1.65697 -1.15162

H 4.88471 2.36265 -0.41540

H 6.34594 2.09377 0.57403

C 3.91992 0.11803 0.15726

H 3.65980 -0.92036 0.39412

O 3.03695 0.97649 -0.03966

Gas phase: E =-2178.210614a.u., G =-2178.271424a.u.

Table S58 StructureA(DMF)···PH3 (in gas phase):

Pd 0.94194 0.15068 0.42652

I 1.27444 -1.69989 -1.52059

C -1.03120 -0.18236 0.30218

C -1.64252 -1.19029 1.04044

C -1.84795 0.56583 -0.53715

C -3.01043 -1.46543 0.95297

C -3.22051 0.33235 -0.66174

C -3.79152 -0.69596 0.08913

P 0.44609 1.73282 2.05953

H -0.29169 1.32297 3.19012

H 1.52192 2.38298 2.70533

H -0.31961 2.85281 1.66956

F -1.30898 1.56878 -1.25906

F -0.90035 -1.93015 1.88101

F -5.10093 -0.93712 -0.01005

Cl -3.73520 -2.73228 1.89570

Cl -4.20667 1.29377 -1.72320

N 5.32288 0.33582 0.28484

C 6.37338 -0.40635 -0.39963

H 5.92969 -1.18112 -1.02741

H 6.96509 0.26429 -1.03256

H 7.04248 -0.88128 0.32664

C 5.73058 1.42286 1.16641

H 6.29238 2.17551 0.60248

H 4.83894 1.87838 1.59375

H 6.36822 1.03866 1.97016

C 4.03079 0.02725 0.10406

H 3.83922 -0.80368 -0.58536

O 3.09320 0.62891 0.66372

P -1.63950 4.74850 -0.31207

H -2.90138 4.31697 -0.79804

H -1.02835 4.75737 -1.59390

H -1.97589 6.13088 -0.34479

Gas phase: E =-2521.331962a.u., G =-2521.399821a.u.

Table S59 Structurets 2A(DMF)(in gas phase):

Pd 0.67937 -0.47395 -0.52556

I 0.86290 -0.38896 2.17752

C -1.26156 0.01837 -0.34910

C -1.66019 1.34811 -0.26957

C -2.25918 -0.94752 -0.28667

C -2.99841 1.72461 -0.12175

C -3.61128 -0.62282 -0.13848

C -3.96860 0.72350 -0.05206

P 0.35981 -0.38202 -2.81331

H -0.02463 0.85251 -3.37942

H 1.45428 -0.68456 -3.65314

H -0.62217 -1.20436 -3.40539

P 2.24200 -2.91793 -0.40041

H 1.55087 -3.95283 0.27680

H 2.95334 -3.78802 -1.27886

H 3.28804 -2.80120 0.54636

F -0.73447 2.32041 -0.34504

F -5.25374 1.05790 0.08558

F -1.92849 -2.24706 -0.38222

Cl -3.45749 3.39851 -0.02873

Cl -4.83048 -1.85936 -0.06793

N 4.79581 1.54376 -0.30839

C 5.35841 2.40716 0.71847

H 4.66051 2.48928 1.55413

H 6.30482 1.99858 1.09170

H 5.54773 3.41058 0.31949

C 5.59068 1.30931 -1.50522

H 5.03374 0.64492 -2.16466

H 6.54861 0.84576 -1.24262

H 5.79164 2.25490 -2.02194

C 3.58089 0.97706 -0.15681

H 3.08576 1.22320 0.79302

O 3.04579 0.23094 -0.98979

Gas phase: E =-2521.321562a.u., G =-2521.387613a.u.

Table S60 StructureAc(in gas phase):

C -0.00001 0.18463 -0.00002

C 1.29262 -0.61447 0.00001

H 1.33981 -1.26692 0.87968

H 1.34034 -1.26597 -0.88034

H 2.14635 0.06421 0.00061

C -1.29261 -0.61449 -0.00001

H -1.33969 -1.26715 -0.87953

H -1.34035 -1.26580 0.88048

H -2.14636 0.06416 -0.00080

O -0.00001 1.40043 0.00000

Gas phase: E =-193.080477a.u., G =-193.109001a.u.

Table S61 Structure2···Ac (in gas phase):

Pd -1.08807 -0.54135 0.66852

I -1.13188 -1.85079 -1.70697

P -3.41355 -1.07617 0.86098

H -3.77132 -2.43996 0.87428

H -4.18808 -0.63113 1.95872

H -4.23617 -0.62936 -0.18808

P -0.85006 0.64887 2.64473

H -0.37352 1.96694 2.52454

H -1.94439 0.86849 3.50775

H 0.08502 0.14535 3.57421

C 0.88880 -0.08669 0.34834

C 1.26642 1.06404 -0.32798

C 1.91222 -0.92927 0.76356

C 2.59709 1.38685 -0.60474

C 3.26204 -0.66084 0.51560

C 3.59201 0.50582 -0.17710

F 1.60379 -2.04871 1.44234

F 4.87307 0.78907 -0.42213

F 0.31010 1.93047 -0.74060

Cl 4.51187 -1.73984 1.05627

Cl 3.01910 2.84540 -1.45254

C -2.62199 2.94975 0.00583

C -2.96539 2.67090 -1.44003

H -2.06775 2.27347 -1.92980

H -3.75616 1.92275 -1.50842

H -3.25628 3.58071 -1.97351

C -1.80604 4.19304 0.29019

H -0.81863 4.08394 -0.17252

H -2.27491 5.07912 -0.15025

H -1.69086 4.33264 1.36636

O -2.94648 2.18211 0.90330

Gas phase: E =-2466.000133a.u., G =-2466.062872a.u.

Table S62 Structurets 2A(Ac)(in gas phase):

Pd -0.95801 -0.18957 0.60452

I -1.16576 -0.55638 -2.07128

P -2.72881 -2.50704 0.88239

H -3.73299 -2.46039 -0.11324

H -3.52797 -3.18155 1.85216

H -2.09488 -3.67675 0.39629

P -0.57715 0.15485 2.86458

H -1.68817 0.23986 3.73347

H 0.18149 -0.81026 3.56001

H 0.12085 1.31156 3.27373

C 1.02509 0.02693 0.35163

C 1.88247 -1.06755 0.32190

C 1.59491 1.28323 0.18326

C 3.25967 -0.93649 0.11865

C 2.96489 1.46844 -0.02286

C 3.78950 0.34287 -0.05835

F 0.81017 2.37891 0.23243

F 5.10177 0.49313 -0.24940

F 1.38419 -2.30185 0.50203

Cl 3.64025 3.05694 -0.22451

Cl 4.30041 -2.32700 0.08898

C -3.72695 1.67674 0.26281

C -5.21548 1.93716 0.22725

H -5.75869 1.11179 0.68862

H -5.54734 2.07133 -0.80860

H -5.44275 2.87066 0.75547

C -2.83402 2.65973 -0.44873

H -1.81276 2.61094 -0.06770

H -3.22813 3.67841 -0.38719

H -2.79552 2.37460 -1.50765

O -3.29087 0.68304 0.83940

Gas phase: E =-2465.980357a.u., G =-2466.043159a.u.

Table S63 Structure 2(in gas phase):

Pd -1.42588 0.71556 0.00524

I -1.80207 -1.96682 -0.01417

P -3.82120 0.87644 0.00605

H -4.49021 0.25265 1.07658

H -4.50884 2.11737 0.01544

H -4.48988 0.26910 -1.07410

P -0.80811 2.95092 0.02101

H -0.00390 3.38303 -1.05244

H -1.75649 4.00121 0.02852

H -0.00372 3.36774 1.10037

C 0.60002 0.38366 0.00290

C 1.31066 0.25586 -1.18302

C 1.31049 0.23745 1.18681

C 2.68031 -0.02226 -1.21479

C 2.68015 -0.04109 1.21443

C 3.35433 -0.17453 -0.00124

F 0.66600 0.37976 2.35972

F 4.66260 -0.43665 -0.00318

F 0.66633 0.41639 -2.35367

Cl 3.53579 -0.21358 2.71645

Cl 3.53614 -0.17146 -2.71919

Gas phase: E =-2272.910619a.u., G =-2272.963273a.u.

Table S64 StructureA(Ac)…PH3 (in gas phase):

Pd -1.07562 0.11088 -0.42867

I -1.26957 -1.18653 1.93325

C 0.91578 -0.07167 -0.29206

C 1.57315 -1.16502 -0.84372

C 1.69680 0.86724 0.37068

C 2.95628 -1.34141 -0.74583

C 3.08318 0.73994 0.49623

C 3.70284 -0.37788 -0.06559

P -0.72019 1.23722 -2.44501

H -0.37881 0.45082 -3.56866

H -1.76607 1.99870 -3.01086

H 0.31917 2.18305 -2.50256

F 1.10708 1.94616 0.91773

F 0.85949 -2.09281 -1.50876

F 5.02576 -0.52088 0.03840

Cl 3.74009 -2.72069 -1.45389

Cl 4.02525 1.93807 1.32998

O -3.27955 0.34071 -0.53712

C -4.14226 -0.53034 -0.67079

C -3.79270 -1.95930 -0.97925

H -4.64756 -2.52682 -1.35280

H -2.96132 -2.00232 -1.68783

H -3.43186 -2.41650 -0.04845

C -5.59073 -0.16769 -0.48404

H -6.15226 -0.38252 -1.40071

H -6.02170 -0.79545 0.30502

H -5.69310 0.88447 -0.21789

P -0.71491 4.50951 -0.21029

H -1.24192 4.05844 1.02764

H -1.35419 5.77950 -0.14594

H 0.50230 4.97669 0.35285

Gas phase: E =-2465.988362a.u., G =-2466.055466a.u.

Table S65 StructureA(Ac) (in gas phase):

Pd 1.13432 0.62653 0.23682

I 1.38593 -1.29099 -1.64273

C -0.84727 0.31727 0.20312

C -1.44496 -0.62252 1.03461

C -1.67925 1.02437 -0.65728

C -2.81976 -0.87436 1.01923

C -3.05999 0.81140 -0.71124

C -3.61888 -0.14990 0.13280

P 0.70372 2.28840 1.81567

H 0.02988 1.92477 3.00060

H 1.76584 3.03226 2.38044

H -0.12504 3.35507 1.41065

F -1.14761 1.95948 -1.46271

F -0.68097 -1.31437 1.89941

F -4.93497 -0.36882 0.10250

Cl -3.52991 -2.05522 2.07716

Cl -4.06799 1.71998 -1.79537

O 3.31017 1.02933 0.20117

C 4.24378 0.29576 0.53538

C 4.02444 -1.01024 1.24628

H 4.90854 -1.33136 1.80186

H 3.15367 -0.94796 1.90331

H 3.78985 -1.76525 0.48433

C 5.65355 0.69549 0.19188

H 6.24596 0.80295 1.10793

H 6.12323 -0.10163 -0.39650

H 5.66233 1.62764 -0.37314

Gas phase: E =-2122.890096a.u., G =-2122.946372a.u.

Table S66 Structure A(MeCN) (in gas phase):

Pd 1.25923 0.66844 0.00143

I 1.57717 -2.01128 -0.00447

P 0.72993 2.94413 0.00676

H -0.04770 3.42912 -1.06501

H -0.04800 3.42351 1.08085

H 1.74546 3.92861 0.00941

C -0.73350 0.36525 0.00077

C -1.44951 0.24829 1.18634

C -1.44965 0.25403 -1.18526

C -2.82794 0.01664 1.21377

C -2.82810 0.02257 -1.21364

C -3.50733 -0.10021 -0.00019

F -0.80301 0.38593 -2.35670

F -4.82448 -0.31654 -0.00062

F -0.80274 0.37461 2.35834

Cl -3.68814 -0.10485 -2.71788

Cl -3.68780 -0.11815 2.71746

C 4.54037 0.77172 0.00150

N 3.39033 0.88628 0.00160

C 5.98350 0.57678 0.00129

H 6.42265 1.01617 -0.89840

H 6.42733 1.04588 0.88350

H 6.20054 -0.49524 0.01849

Gas phase: E =-2062.501499a.u., G =-2062.559747a.u

Table S67 StructureA(MeCN)···PH3 ( in gas phase):

Pd 0.76501 -0.89985 0.41631

I 1.36612 0.86027 -1.54214

P -0.00751 -2.35582 2.07021

H -0.99532 -3.29085 1.69761

H 0.88279 -3.22628 2.74071

H -0.65023 -1.78835 3.19008

C -1.15184 -0.29598 0.26318

C -2.04343 -0.91034 -0.60818

C -1.63327 0.77120 1.01233

C -3.36829 -0.48765 -0.75225

C -2.94832 1.23338 0.90726

C -3.80821 0.59447 0.01212

F -0.81200 1.38425 1.88311

F -5.06998 1.01422 -0.10382

F -1.62850 -1.96012 -1.33852

Cl -3.51305 2.56767 1.86632

Cl -4.45331 -1.28501 -1.85021

C 3.97510 -1.58850 0.47205

N 2.82819 -1.45705 0.53198

C 5.42231 -1.70508 0.36950

H 5.85025 -0.69683 0.36502

H 5.82085 -2.27053 1.21601

H 5.68612 -2.21485 -0.56131

P 5.17707 2.29325 0.28490

H 3.96635 2.75935 0.85828

H 4.91128 2.84169 -0.99637

H 5.95058 3.40389 0.72528

Gas phase: E =-2405.623109a.u., G =-2405.689783a.u.

Table S68 Structure2···MeCN (in gas phase):

Pd -1.18335 -0.43113 0.66577

I -1.45084 -0.93818 -1.99135

P -3.52440 -0.91878 0.86333

H -3.92745 -2.22585 0.52308

H -4.20836 -0.79030 2.09637

H -4.40395 -0.18395 0.04755

P -0.77812 0.23036 2.84878

H -0.24300 1.52330 2.99121

H -1.82610 0.30001 3.79161

H 0.16418 -0.50814 3.59464

C 0.82108 -0.09254 0.37776

C 1.32728 1.14396 0.00361

C 1.73650 -1.12938 0.50934

C 2.68338 1.36550 -0.25163

C 3.10406 -0.96798 0.26824

C 3.56560 0.29181 -0.11864

F 1.29981 -2.34327 0.89235

F 4.86661 0.47504 -0.35210

F 0.48452 2.19343 -0.11561

Cl 4.21536 -2.29122 0.44690

Cl 3.27230 2.93280 -0.71955

C -2.62248 2.84731 0.36333

N -2.88683 2.48388 1.43458

C -2.28814 3.27620 -0.99091

H -2.18106 2.39529 -1.63217

H -3.07389 3.92491 -1.38714

H -1.33859 3.81627 -0.98571

Gas phase: E =-2405.632774a.u., G =-2405.691321a.u.

Table S69 Structurets 2A(MeCN) (in gas phase):

Pd 1.07716 0.27644 0.66876

I 1.45241 -0.48454 -1.91277

P 2.82774 2.58654 0.05352

H 2.16060 3.33829 -0.94376

H 3.47576 3.70739 0.65220

H 3.92813 2.22080 -0.76075

P 0.54411 0.83168 2.85697

H -0.13777 -0.11921 3.64581

H 1.60115 1.14754 3.73796

H -0.29340 1.94385 3.08468

C -0.89735 0.07215 0.35536

C -1.53171 -1.15355 0.52255

C -1.67953 1.14565 -0.05359

C -2.89846 -1.32708 0.28465

C -3.04954 1.02273 -0.30444

C -3.64809 -0.22683 -0.13523

F -1.11251 2.35501 -0.20825

F -4.95507 -0.36860 -0.36511

F -0.81996 -2.21600 0.93476

Cl -3.99658 2.38805 -0.81149

Cl -3.66010 -2.87296 0.50584

C 3.82581 -1.50302 0.86335

N 3.28107 -0.65286 1.43634

C 4.46212 -2.56161 0.09350

H 5.51713 -2.33050 -0.07566

H 3.94713 -2.63095 -0.87093

H 4.38043 -3.51687 0.61881

Gas phase: E =-2405.611773a.u., G =-2405.674676a.u.

Table S70 Structurets 2A(THF) (in gas phase):

Pd 0.81697 -0.37383 0.57644

C -1.14252 -0.00593 0.32220

C -2.07394 -1.03465 0.24814

C -1.61905 1.29462 0.20383

C -3.43812 -0.79909 0.05229

F -1.66322 -2.30863 0.38118

C -2.97265 1.58304 0.00742

F -0.75757 2.32487 0.29071

C -3.87514 0.52075 -0.07215

Cl -4.57465 -2.11036 -0.02982

Cl -3.53322 3.22148 -0.13220

F -5.17304 0.77075 -0.25542

I 1.07770 -0.35551 -2.11034

P 2.29242 -2.88660 0.57893

P 0.39752 -0.31969 2.85963

H 3.17805 -3.09594 -0.50662

H 1.29643 -3.78186 0.12134

H 2.92226 -3.82221 1.45181

H 1.47734 -0.48802 3.75521

H -0.49280 -1.27671 3.39134

H -0.17966 0.84078 3.41904

H 2.03238 2.36322 0.54171

C 2.94500 2.09183 1.08310

O 3.12310 0.65364 0.99018

C 4.19115 2.71914 0.45165

H 2.81935 2.35344 2.13986

C 4.27677 0.35639 0.16681

C 4.60416 1.65199 -0.57300

H 4.97774 2.85799 1.20198

H 3.97802 3.69169 0.00021

H 5.10195 0.04206 0.82101

H 4.01349 -0.46450 -0.50343

H 5.65709 1.71393 -0.86152

H 3.99024 1.72901 -1.47567

Gas phase: E =-2505.239861a.u., G =-2505.303972a.u.

Table S71 StructureA(THF)···PH3 (in gas phase):

Pd -1.01813 0.16713 0.48743

C 0.93597 -0.21927 0.28100

C 1.74982 0.55906 -0.53268

C 1.53422 -1.29271 0.93189

C 3.10914 0.29154 -0.71768

F 1.22076 1.62590 -1.16601

C 2.88873 -1.60388 0.78147

F 0.79268 -2.06098 1.74758

C 3.66774 -0.80269 -0.05542

Cl 4.09342 1.29102 -1.74421

Cl 3.59946 -2.95200 1.61444

F 4.96422 -1.07731 -0.21321

I -1.51787 -1.54814 -1.53177

P -0.41846 1.62327 2.20849

H -1.43596 2.26612 2.94972

H 0.34867 1.10372 3.27201

H 0.37436 2.73937 1.86349

C -3.84162 1.39110 -0.32643

C -5.31340 -0.36948 0.30002

C -5.32868 1.10082 -0.14970

H -3.46903 1.04150 -1.29459

H -3.56552 2.43930 -0.18410

H -5.18611 -1.02788 -0.56441

H -6.22138 -0.66711 0.83088

H -5.88959 1.25864 -1.07446

H -5.75908 1.74230 0.62725

O -3.18942 0.62511 0.72745

C -4.07516 -0.43994 1.19562

H -4.30489 -0.22889 2.24624

H -3.54096 -1.38858 1.11845

P 1.72904 4.71307 0.02016

H 1.13806 4.86905 -1.26177

H 2.97310 4.25840 -0.48985

H 2.13761 6.07243 0.11615

Gas phase: E =-2505.251092a.u., G =-2505.316531a.u.

Table S72 Structure2···THF (in gas phase):

Pd 0.69246 -0.75951 0.58113

C -1.12633 0.15451 0.31887

C -2.27162 -0.33363 0.93448

C -1.27956 1.25882 -0.50749

C -3.53517 0.23106 0.73733

F -2.17106 -1.38861 1.76360

C -2.51707 1.86558 -0.74097

F -0.19384 1.78456 -1.11221

C -3.64429 1.33413 -0.11189

Cl -4.94460 -0.40959 1.52686

Cl -2.66402 3.25069 -1.78153

F -4.83841 1.89557 -0.31428

I 0.15489 -2.35543 -1.54387

P 2.79556 -1.89406 0.74484

P 0.99983 0.77220 2.29264

H 3.67147 -1.74158 -0.34581

H 3.70707 -1.64328 1.79812

H 2.75674 -3.30114 0.81478

H 2.13565 0.73232 3.12837

H 1.02784 2.12576 1.90989

H -0.01127 0.82745 3.27520

H 2.91186 0.87472 -1.32018

C 3.23101 1.73560 -0.72642

O 3.59522 1.26760 0.59517

C 4.47057 2.44433 -1.27405

H 2.37938 2.42267 -0.64376

C 4.81688 1.90408 1.01822

C 5.09256 3.02111 0.00685

H 4.22195 3.20543 -2.01809

H 5.15266 1.72429 -1.73990

H 4.68768 2.26997 2.04314

H 5.62671 1.16070 1.02040

H 4.57407 3.94064 0.30027

H 6.15775 3.24858 -0.08740

Gas phase: E =-2505.259604a.u., G =-2505.323552a.u.

Table S73 Structurets 2A(PhCl) (in gas phase):

Pd 0.43767 -0.69738 -0.41869

I 0.37748 -0.93434 2.25340

P 0.90622 -3.80413 -0.52682

H -0.40533 -4.14487 -0.11631

H 1.53457 -4.20970 0.67626

H 1.14667 -5.02633 -1.22043

P 0.32197 -0.38084 -2.72965

H -0.76885 -0.96644 -3.40543

H 0.20282 0.93612 -3.22236

H 1.37556 -0.83790 -3.55181

C -1.37337 0.15419 -0.31810

C -1.51984 1.52062 -0.10840

C -2.53048 -0.60476 -0.44771

C -2.77533 2.13025 -0.02353

C -3.80718 -0.04049 -0.36971

C -3.91504 1.33412 -0.15151

F -2.43128 -1.92730 -0.66900

F -5.12240 1.89630 -0.07781

F -0.42850 2.29263 0.00986

Cl -5.23251 -1.01669 -0.54391

Cl -2.92585 3.84090 0.23350

C 4.18481 2.63719 0.90137

C 5.14654 3.12224 0.01291

C 5.54564 2.34460 -1.07569

C 4.98571 1.08231 -1.28415

C 4.02803 0.62361 -0.38251

C 3.61430 1.37613 0.71364

H 3.87125 3.23770 1.74980

H 5.58450 4.10335 0.16862

H 6.29474 2.71573 -1.76877

H 5.28977 0.46709 -2.12404

H 2.86635 0.98776 1.39660

Cl 3.32410 -0.98631 -0.64083

Gas phase: E =-2964.644648a.u., G =-2964.711596a.u.

Table S74 StructureA(PhCl) (in gas phase):

Pd -0.62462 0.18050 -0.06330

I 0.13311 2.74612 -0.05069

P -1.07693 -2.11552 -0.13263

H -0.41468 -2.85108 -1.13658

H -0.70725 -2.88839 0.98829

H -2.39172 -2.59952 -0.31917

C 1.31337 -0.32963 -0.00812

C 1.98740 -0.45494 1.20098

C 2.03075 -0.56396 -1.17489

C 3.34157 -0.79675 1.26583

C 3.38587 -0.90780 -1.16033

C 4.03248 -1.01588 0.07237

F 1.40664 -0.47436 -2.36097

F 5.32390 -1.34741 0.11109

F 1.32355 -0.25390 2.34985

Cl 4.25228 -1.20198 -2.63582

Cl 4.15465 -0.95119 2.79183

Cl -3.12672 1.07351 -0.08767

C -4.32482 -0.22985 0.02541

C -4.66595 -0.72522 1.28255

C -4.90365 -0.71623 -1.14501

C -5.61788 -1.74444 1.36191

H -4.20333 -0.31891 2.17548

C -5.85416 -1.73520 -1.04552

H -4.62256 -0.30363 -2.10789

C -6.21079 -2.24963 0.20278

H -5.89632 -2.13817 2.33468

H -6.31626 -2.12207 -1.94864

H -6.95148 -3.04011 0.27237

Gas phase: E =-2621.524589a.u., G =-2621.587923a.u.

Table S75 Structure2···PhCl (in gas phase):

Pd -0.07263 0.80942 0.54847

I -1.19906 2.68700 -1.04842

P 1.77053 2.33181 0.76163

H 1.46640 3.62088 1.24077

H 2.90207 2.05716 1.56930

H 2.43288 2.67409 -0.43212

P 0.64726 -0.94665 1.87948

H -0.22695 -1.33004 2.91617

H 0.82013 -2.19127 1.24233

H 1.85840 -0.89263 2.60664

C -1.72288 -0.37293 0.24217

C -1.81231 -1.21365 -0.85959

C -2.81560 -0.33243 1.09739

C -2.94685 -1.98472 -1.12920

C -3.97546 -1.08118 0.87693

C -4.02881 -1.90353 -0.25015

F -2.76194 0.44827 2.19341

F -5.12253 -2.63229 -0.48252

F -0.76846 -1.30296 -1.70293

Cl -5.32181 -1.00586 1.97315

Cl -3.02132 -3.02665 -2.51763

C 7.26649 -2.07268 0.95287

C 8.18020 -1.36638 0.16872

C 7.71947 -0.48981 -0.81537

C 6.34993 -0.31243 -1.02061

C 5.45439 -1.02574 -0.22540

C 5.89344 -1.90747 0.76078

H 7.61812 -2.75860 1.71776

H 9.24647 -1.50013 0.32224

H 8.42490 0.06026 -1.43090

H 5.98224 0.36251 -1.78558

H 5.17683 -2.45672 1.36152

Cl 3.72120 -0.80907 -0.48323

Gas phase: E =-2964.666248 a.u., G =-2964.733582 a.u.

Table S76 StructureA(PhCl)···PH3 (in gas phase):

Pd -0.56225 -0.20798 0.20281

I 0.21994 -1.48610 2.42216

P -1.06085 0.96614 -1.76562

H -0.25068 2.07509 -2.07084

H -0.94506 0.25403 -2.97984

H -2.33719 1.53879 -1.95255

C 1.36567 -0.04875 -0.31559

C 1.97398 -1.01536 -1.10758

C 2.14440 1.02327 0.10186

C 3.31878 -0.93562 -1.48186

C 3.49238 1.14780 -0.24677

C 4.07067 0.15398 -1.03888

F 1.59284 1.98409 0.86394

F 5.35459 0.25374 -1.38717

F 1.25123 -2.06004 -1.54420

Cl 4.43588 2.50459 0.28629

Cl 4.04575 -2.15683 -2.47908

Cl -3.06867 -0.55157 1.02623

C -4.23308 -0.30925 -0.28980

C -4.35400 -1.29204 -1.27074

C -5.00661 0.84945 -0.30200

C -5.28116 -1.09825 -2.29728

H -3.74359 -2.18760 -1.22731

C -5.93008 1.02417 -1.33565

H -4.89322 1.59272 0.47944

C -6.06743 0.05544 -2.33174

H -5.38879 -1.85652 -3.06685

H -6.54163 1.92103 -1.35695

H -6.78743 0.19765 -3.13155

P -1.01553 4.08548 0.67991

H 0.17870 4.85224 0.73640

H -0.86005 3.54449 1.98223

H -1.84755 5.15945 1.10435

Gas phase: E =-2964.645755a.u., G =-2964.715788a.u.