This journal is © The Royal Society of Chemistry 1999

Theoretical study on linear dicyanide and dicarbonyl complexes of the metals Au, Hg, and Tl: On the possible existence of a [Tl(CO)2]3+ cation

Volker Jonas and Walter Thiel*

Organisch-Chemisches Institut, Universität Zürich, Winterthurerstrasse 190,

CH-8057 Zürich, Switzerland

Supplementary Material

Tables S1 – S8

Table S1 Experimental and Calculated Bond Lengths (in Å) for [Au(CN)2]-, [Hg(CN)2], [Tl(CN)2]+,

[Au(CO)2]+, [Hg(CO)2]2+, and [Tl(CO)2]3+

______

[Au(CN)2]-[Hg(CN)2][Tl(CN)2]+

______

Au-CC-NHg-CC-NTl-CC-N

______

exp.2.019(12)a1.106(14)a2.015(3)d1.137(3)de

1.979(12)b1.167(16)b

1.982(19)c1.123(27)c

BP86/ECP11.9961.1832.0191.1772.0471.179

MP2/ECP11.9991.1892.0171.1852.0271.190

CCSD(T)/ECP12.0191.1822.0311.1772.0421.180

______

______

[Au(CO)2]+[Hg(CO)2]2+[Tl(CO)2]3+

______

Au-CC-OHg-CC-OTl-CC-O

______

exp.2.083(10)f1.104(12)f

BP86/ECP11.9881.1392.1161.1312.2571.132

MP2/ECP12.0301.1362.1481.1312.2321.132

CCSD(T)/ECP12.0161.1222.1301.1162.2031.117

______

a Reference 45a, average values for [LysineH][Au(CN)2]. Specific values: Au-C1 2.022(12) Å, Au-C2 2.015(12) Å; C1-N1 1.100(14) Å, C2-N2 1.112(14) Å.

b Reference 45b, values for [2,7-bis(methylseleno)-1,6-dithiapyrene][Au(CN)2].

c Reference 45c, values for [Au{(Ph2PCH2)2AsPh}2][Au(CN)2].

d Reference 46, values corrected for thermal motion are: Hg-C 2.019(3) Å, C-N 1.160(3) Å.

e Reference 28c gives a value of 2.11(2) Å for trans-[Tl(CN)2(OH2)4]+ in aqueous solution, obtained from large-angle X-ray scattering.

f Reference 5b, values for [Hg(CO)2][Sb2F11]2.

Table S2 Vibrational Frequencies (in cm-1) for [Au(CN)2]-, [Hg(CN)2] and [Tl(CN)2]+

______

Exp. ia,b,c BP86MP2CCSD(T)

(solution)ECP1ECP1ECP1

______

[Au(CN)2]-

g+1[CN]21612161 02103-582189+28

g+2[MC]446432-14430-16414-32

u+3[CN]21422145+ 32091-512176+24

u+4[MC]426412-14409-17395-31

g5[MCN]301276-25264-37260-41

u6[MCN]410417+ 7388-22377-33

u7[CMC]12577-4877-4876-49

______

[Hg(CN)2]

g+1[CN]21972212+152126-712226+29

g+2[MC]412419+ 7436+24426+14

u+3[CN]21972212+152123-742223+26

u+4[MC]442454+12467+25457+15

g5[MCN]276238-38224-52223-53

u6[MCN]341349+ 8330-11325-16

u7[CMC]757372

______

[Tl(CN)2]+

g+1[CN]21872192+ 52083-1032200+13

g+2[MC]390384- 6432+42417+27

u+3[CN]21992198- 12084-1152201+ 2

u+4[MC]345d472500487

g5[MCN]207184180

u6[MCN]300278273

u7[CMC]676664

______

a Solution values for K[Au(CN)2], Reference 24. IR data from 1-methyl-2-pyrrolidone solution; Raman data from aqueous solution.

b References 23, 26, 27 for [Hg(CN)2]; IR values from solid state (mineral oil mull), Raman values from aqueous solution.

c Reference 28c for [Tl(CN)2]+; IR and Raman data in aqueous solution, bands attributed to trans-[Tl(CN)2(OH2)4]+.

d Assignment inconsistent with present theoretical results.

Table S3 Vibrational Frequencies (in cm-1) for [Au(CO)2]+, [Hg(CO)2]2+ and [Tl(CO)2]3+

______

Exp. ia,bBP86MP2CCSD(T)

(solid)ECP1ECP1ECP1

______

[Au(CO)2]+

g+1[CO]22542232-222201-532268+14

g+2[MC]400403+ 3374-26355- 45

u+3[CO]22172192-252176-412242+25

u+4[MC]354353- 1325-29313- 41

g5[MCO]312298-14299-13292- 20

u6[MCO]406399- 7390-16379- 27

u7[CMC]10560-4565-4064- 41

______

[Hg(CO)2]2+

g+1[CO]22812280- 12195-862296+15

g+2[MC]315317304

u+3[CO]22782276- 22197-812295+17

u+4[MC]348357346

g5[MCO]285286282

u6[MCO]335347+12339+ 4331- 4

u7[CMC]656462

______

[Tl(CO)2]3+

g+1[CO]225421122264

g+2[MC]245315290

u+3[CO]225621152265

u+4[MC]321374350

g5[MCO]278283278

u6[MCO]316322314

u7[CMC]596360

______

a Reference 10b; values for solid [Au(CO)2][Sb2F11].

b Reference 5b; values for solid [Hg(CO)2][Sb2F11]2.

Table S4 Experimental Relative and Calculated Infrared Intensities (in km/mol) for [Au(CN)2]-,

[Hg(CN)2], [Tl(CN)2]+, [Au(CO)2]+, [Hg(CO)2]2+, and [Tl(CO)2]3+ a

______

exp.bBP86MP2CCSD(T)exp.cBP86MP2CCSD(T)

______

[Au(CN)2]-[Au(CO)2]+

______

u+3[CX]s50.15.614.6s475.8191.3272.8

u+4[MC]m14.413.519.0w47.644.433.1

u6[MCX]sh0.50.00.3m10.46.311.1

u7[CMC] m,bd28.529.730.9vw0.60.70.5

______

[Hg(CN)2][Hg(CO)2]2+

______

u+3[CX]vs52.490.564.5m13.414.31.0

u+4[MC]s40.443.646.20.50.20.3

u6[MCX]m0.31.51.4m18.89.213.7

u7[CMC]19.723.924.03.32.51.9

______

[Tl(CN)2]+[Tl(CO)2]3+

______

u+3[CX]289.3326.6304.724.0161.733.0

u+4[MC]23.931.731.13.80.10.7

u6[MCX]2.94.86.024.311.717.9

u7[CMC]8.113.212.18.55.74.9

______

a All calculated data were obtained from the ECP1 calculations; X = O or N, respectively.

b Reference 24 for [Au(CN)2]-; Reference 26 for [Hg(CN)2].

c Reference 10b for [Au(CO)2]+; Reference 5b for [Hg(CO)2]2+.

Table S5 Experimental Relative and Calculated Raman Intensities (in Å4/amu) for [Au(CN)2]-, [Hg(CN)2], [Tl(CN)2]+, [Au(CO)2]+, [Hg(CO)2]2+, and [Tl(CO)2]3+ a

______

[Au(CN)2]-[Hg(CN)2][Tl(CN)2]+

______

exp.bcalc.exp.bcalc.calc.

______

g+1[CN]35518.513.7271.9110.8

g+2[MC]0.81.73.619.798.5

g5[MCN]611.25.85.510.1

______

______

[Au(CO)2]+[Hg(CO)2]2+[Tl(CO)2]3+

______

exp.ccalc.exp.dcalc.calc.

______

g+1[CO]vs228.0s86.345.3

g+2[MC]vw2.28.877.7

g5[MCO]sh0.51.30.5

______

a All data at BP86/ECP2.

b Reference 26b; peak intensities at maximum for a 1 molar aqueous solution.

c Reference 10b; 5 is weak in HSO3F solution.

d Reference 5b; due to overlap with the counterion bands 2 and 5 were not assigned.

Table S6 Experimental and Calculated Isotopic Shifts (in cm-1) for [Au(CN)2]-, [Hg(CN)2], [Tl(CN)2]+, [Au(CO)2]+, [Hg(CO)2]2+, and [Tl(CO)2]3+ a

______

Exp. IbCalc.IExp. IbCalc.IExp. IcCalc.IExp. IcCalc.I

13C14N13C14N12C15N12C15N13C16O13C16O12C18O12C18O

______

[Au(CN)2]-[Au(CO)2]+

______

g+1[CX]48.448.530.430.451.552.94949.5

g+2[MC]7.38.56.56.51014.6

u+3[CX]46.447.130.431.050.550.15251.2

u+4[MC]5.66.44.54.799.8

g5[MCX]8.22.49.08.93.53.9

u6[MCX]13.81.51413.132.9

u7[CMC]0.12.000.152.5

______

[Hg(CN)2][Hg(CO)2]2+

______

g1[CX]49.149.930.930.95353.252.0

g2[MC]7.28.45.211.3

u3[CX]48.249.730.631.15352.852.1

u4[MC]6.17.34.59.8

g5[MCX]6.82.08.33.8

u6[MCX]11.71.11011.12.7

u7[CMC]0.22.00.22.7

______

[Tl(CN)2]+[Tl(CO)2]3+

______

g1[CX]49.430.952.152.3

g2[MC]6.77.84.28.9

u3[CX]50.030.552.451.9

u4[MC]6.27.84.29.1

g5[MCX]5.61.78.03.9

u6[MCX]10.00.89.92.9

u7[CMC]0.11.80.32.5

______

a Shifts relative to 12C14N and 12C16O, respectively. X = O or N, respectively. Calculated values at BP86/ECP2.

b References 23, 25 for [Au(CN)2]-. References 23, 27 for [Hg(CN)2].

c References 10b and 5b, values for solid [Au(CO)2][Sb2F11] and [Hg(CO)2][Sb2F11]2.

TABLE S7 Harmonic Symmetry Force Constants Fij for [Au(CN)2]-, [Hg(CN)2], and [Tl(CN)2]+ a

______

[Au(CN)2]-
______/ [Hg(CN)2]
______/ [Tl(CN)2]+
______
exp.b / BP86 / MP2 / CCSD(T) / exp.c / BP86 / MP2 / CCSD(T) / BP86d / MP2 / CCSD(T)

______

F1,1 / 17.67 ± 0.18 / 17.04 / 16.04 / 17.36 / 18.07 ± 0.2 / 17.73 / 16.22 / 17.81 / 17.42 / 15.49 / 17.39
F1,2 / 0.32 ± 0.1 / 0.22 / 0.15 / 0.08 / 0.05 ± 0.1 / -0.01 / -0.05 / -0.09 / -0.12 / -0.16 / -0.16
F2,2 / 3.20 ± 0.03 / 2.91 / 3.17 / 2.92 / 2.71 ± 0.03 / 2.79 / 3.23 / 3.06 / 2.43 / 3.33 / 3.11
F3,3 / 17.61 ± 0.18 / 17.00 / 16.04 / 17.32 / 18.07 ± 0.2 / 17.75 / 16.25 / 17.82 / 17.44 / 15.52 / 17.39
F3,4 / 0.31 ± 0.15 / 0.18 / 0.07 / 0.02 / 0.05 ± 0.1 / -0.04 / -0.09 / -0.13 / -0.05 / -0.10 / -0.11
F4,4 / 2.36 ± 0.03 / 2.06 / 2.18 / 2.02 / 2.47 ± 0.03 / 2.59 / 2.84 / 2.69 / 2.90 / 3.41 / 3.21
F5,5 / 0.23 / 0.25 / 0.25 / 0.16 / 0.17 / 0.16 / 0.11 / 0.11 / 0.11
F6,6 / 0.26 / 0.28 / 0.27 / 0.17 / 0.17 / 0.17 / 0.12 / 0.12 / 0.11
F6,7 / -0.14 / -0.13 / -0.12 / -0.08 / -0.07 / -0.07 / -0.06 / -0.06 / -0.05
F7,7 / 0.56 / 0.47 / 0.45 / 0.52 / 0.43 / 0.41 / 0.43 / 0.42 / 0.39

______

a All calculated data were obtained from the ECP2 calculations. For the notation of force constants see Reference 23, p. 117 ff. See text for units.

b References 23, 25; c References 23, 27; the experimental symmetry force constants were calculated from the experimental internal force constants.

d Reference 28c gives empirical values of 17.62 mdyn Å-1 for F1,1 and 2.34 mdyn Å-1 for F2,2.

TABLE S8 Harmonic Symmetry Force Constants Fij for [Au(CO)2]+, [Hg(CO)2]2+, and [Tl(CO)2]3+ a

______

[Au(CO)2]+
______/ [Hg(CO)2]2+
______/ [Tl(CO)2]3+
______
exp.b / BP86 / MP2 / CCSD(T) / exp. / BP86 / MP2 / CCSD(T) / BP86 / MP2 / CCSD(T)

______

F1,1 / 20.25 ± 0.1 / 19.51 / 19.16 / 20.26 / 20.49 / 19.14 / 20.77 / 20.16 / 17.85 / 20.33
F1,2 / 0.45 ± 0.2 / 0.20 / 0.14 / 0.06 / -0.06 / -0.03 / -0.11 / -0.16 / 0.00 / -0.10
F2,2 / 2.70 ± 0.03 / 2.80 / 2.72 / 2.44 / 1.74 / 1.89 / 1.75 / 1.09 / 1.83 / 1.59
F3,3 / 19.95 ± 0.1 / 19.42 / 19.16 / 20.21 / 20.49 / 19.19 / 20.77 / 20.17 / 17.91 / 20.33
F3,4 / 0.45 ± 0.2 / 0.41 / 0.27 / 0.20 / -0.02 / -0.02 / -0.09 / -0.08 / 0.05 / -0.06
F4,4 / 1.62 ± 0.03 / 1.67 / 1.54 / 1.42 / 1.62 / 1.75 / 1.62 / 1.43 / 1.94 / 1.72
F5,5 / 0.253 ± 0.02 / 0.25 / 0.28 / 0.27 / 0.22 / 0.24 / 0.23 / 0.22 / 0.24 / 0.23
F6,6 / 0.283 ± 0.02 / 0.28 / 0.31 / 0.29 / 0.23 / 0.25 / 0.24 / 0.22 / 0.25 / 0.24
F6,7 / -0.02 ± 0.02 / -0.12 / -0.12 / -0.11 / -0.06 / -0.05 / -0.04 / -0.03 / -0.03 / -0.03
F7,7 / 0.77 ± 0.09 / 0.31 / 0.25 / 0.24 / 0.32 / 0.23 / 0.22 / 0.26 / 0.25 / 0.23

______

a All calculated data were obtained from the ECP2 calculations. For the notation of force constants see Reference 23, p. 117 ff. See text for units.

b Reference 10b. The experimental symmetry force constants were calculated from the experimental internal force constants.