Electronic Supplementary Material for

Theoretical study of the Fe+-mediated oxidation of ethane by N2O

Lianming Zhao*a, Wenyue Guo*a, Zhaochun Liu,a Yuanyuan Li,a and Xiaoqing Lub

a College of Physics Science and Technology, China University of Petroleum

Dongying, Shandong 257061, PR China

b Department of Physics and Materials Science, City University of Hong Kong, Hong Kong SAR, PR China

(Correspondence should be addressed to and )

Theoretical Chemistry Accounts

Index

Figure S1 S3

Figure S2 S6

Figure S3 S7

Figure S4 S8

Figure S5 S10

Figure S6 S11

Figure S7 S12

Figure S8 S13

Figure S9 S14

Figure S10 S15

Figure S11 S16

Table S1. S17

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Figure S1 Optimized geometries and selected structural parameters (Å and deg) for all the intermediates, saddle points and products involved in the C2H6 oxidation by FeO+ associated with the Fe+-mediated oxidation of ethane by N2O at the B3LYP/DZVP(opt+3f):6-311+G(2d,2p) level.

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Figure S1 Continued.

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Figure S1 Continued.

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Figure S2 Energy profile for the conversion of OFe+(C2H6) to (C2H5)Fe+(OH) via stepwise H-shift associated with the Fe+-mediated oxidation of ethane by N2O at the B3LYP/DZVP(opt+3f):6-311+G(2d,2p) level.

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Figure S3 Optimized geometries and selected structural parameters (Å and deg) for all the intermediates, saddle points and products involved in the N2O reduction by FeC2H4+ associated with the Fe+-mediated oxidation of ethane by N2O at the B3LYP/DZVP(opt+3f):6-311+G(2d,2p) level.

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Figure S4 Optimized geometries and selected structural parameters (Å and deg) for all the intermediates, saddle points and products for the loss of acetaldehyde and oxirane from (C2H4)FeO+ via the cyclization mechanism involved in the FeC2H4+ oxidation by N2O associated with the Fe+-mediated oxidation of ethane by N2O at the B3LYP/DZVP(opt+3f):6-311+G(2d,2p) level.

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Figure S4 Continued.

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Figure S5 Energy profile for the conversion of metallaoxacyclobutane to Fe+(acetaldehyde) via Fe+-mediated H-shift, and the subsequent formation of FeCO+ associated with the Fe+-mediated oxidation of ethane by N2O at the B3LYP/DZVP(opt+3f):6-311+G(2d,2p) level.

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Figure S6 Optimized geometries and selected structural parameters (Å and deg) for all the intermediates, saddle points and products for the loss of ethanol from (C2H4)FeO+ via the direct hydrogen abstraction mechanisms involved in the FeC2H4+ oxidation by N2O associated with the Fe+-mediated oxidation of ethane by N2O at the B3LYP/DZVP(opt+3f):6-311+G(2d,2p) level.

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Figure S7 Energy profile for the loss of ethanol from (C2H4)FeO+ via the cyclization mechanism involved in the FeC2H4+ oxidation by N2O associated with the Fe+-mediated oxidation of ethane by N2O at the B3LYP/DZVP(opt+3f):6-311+G(2d,2p) level.

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Figure S8 Energy profile for the formation of FeOH+ from (C2H4)FeO+ involved in the FeC2H4+ oxidation by N2O associated with the Fe+-mediated oxidation of ethane by N2O at the B3LYP/DZVP(opt+3f):6-311+G(2d,2p) level.

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Figure S9 Energy profile for the formation of FeCH2+ from (C2H4)FeO+ involved in the FeC2H4+ oxidation by N2O associated with the Fe+-mediated oxidation of ethane by N2O at the B3LYP/DZVP(opt+3f):6-311+G(2d,2p) level.

Figure S10 Energy profile for the FeC2H2+ formation involved in the FeC2H4+ oxidation by N2O associated with the Fe+-mediated oxidation of ethane by N2O at the B3LYP/DZVP(opt+3f):6-311+G(2d,2p) level.

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Figure S11 Optimized geometries and selected structural parameters (Å and deg) for all the intermediates, saddle points and products involved in the FeOH2+ oxidation by N2O associated with the Fe+-mediated oxidation of ethane by N2O at the B3LYP/DZVP(opt+3f):6-311+G(2d,2p) level.

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TSBLE S1 Calculated energies E (in hartrees), zero-point energies ZPE (in hartrees), and <S2> at the B3LYP/DZVP(opt+3f):6-311++G(2d,2p) level for all species involved in the Fe+-mediated oxidation of ethane by N2O.

Species / E / ZPE / <S2a / Species / E / ZPE / <S2a
C2H6 / -79.86098 / 0.07451 / 0.00 / H2O / -76.46204 / 0.02139 / 0.00
C2H4 / -78.61959 / 0.05093 / 0.00 / C2H5OH / -155.10176 / 0.07975 / 0.00
N2O / -184.72430 / 0.01106 / 0.0 / N2 / -109.56348 / 0.00555 / 0.0
CH3CHO / -153.88762 / 0.05532 / 0.0 / CH2CHOH / -153.86997 / 0.05617 / 0.0
CH2CH / -77.93250 / 0.03640 / 0.76 / c-CH2CH2O / -153.84181 / 0.05725 / 0.0
CH2O / -114.54518 / 0.02653 / 0.0 / CH4 / -40.53671 / 0.04468 / 0.0
6Fe+ / -1263.18164 / 0.0 / 8.75 / 4Fe+ / -1263.16174 / 0.0 / 4.40
6FeO+ / -1338.39621 / 0.00197 / 8.77 / 4FeO+ / -1338.38293 / 0.00153 / 4.48
6FeCH2+ / -1302.45250 / 0.02043 / 8.77 / 4FeCH2+ / -1302.48179 / 0.02454 / 4.28
6FeC2H4+ / -1341.83949 / 0.05211 / 8.76 / 4FeC2H4 / -1341.87534 / 0.05261 / 3.81
6FeOH2+ / -1339.69629 / 0.02343 / 8.75 / 4FeOH2+ / -1339.69401 / 0.02449 / 4.07
5FeOH+ / -1339.08098 / 0.01163 / 6.01 / 3FeOH+ / -1339.01829 / 0.01158 / 3.00
6FeCO+ / -1376.55428 / 0.00609 / 8.75 / 4FeCO+ / -1376.58952 / 0.00784 / 3.79
6FeC2H2+ / -1340.57737 / 0.02749 / 8.75 / 4FeC2H2+ / -1340.61492 / 0.02829 / 3.82
61a / -1418.30491 / 0.07674 / 8.77 / 41a / -1418.29965 / 0.07647 / 4.37
61b / -1418.30373 / 0.07710 / 8.77 / 41b / -1418.29479 / 0.07681 / 4.44
6TS1a-2 / -1418.26311 / 0.07095 / 8.77 / 4TS1a-2 / -1418.27395 / 0.07310 / 3.83
6TS1b-2 / -1418.25908 / 0.07198 / 8.77 / 4TS1b-2 / -1418.26470 / 0.07267 / 3.93
62 / -1418.33687 / 0.07443 / 8.76 / 42 / -1418.34559 / 0.07461 / 4.05
6TS2-3 / -1418.29577 / 0.07383 / 8.76 / 4TS2-3 / -1418.30567 / 0.07637 / 4.11
63 / -1418.35011 / 0.08102 / 8.75 / 43 / -1418.34227 / 0.08127 / 4.11
6TS2-4 / -1418.29610 / 0.07024 / 8.77 / 4TS2-4 / -1418.33016 / 0.07079 / 3.87
64 / -1418.31382 / 0.07095 / 8.76 / 44 / -1418.33380 / 0.07140 / 3.86
6TS4-5 / -1418.26312 / 0.06920 / 8.76 / 4TS4-5 / -1418.32336 / 0.07090 / 3.88
65 / -1418.34177 / 0.07618 / 8.76 / 45 / -1418.40174 / 0.07713 / 3.81
66 / -1526.58079 / 0.06413 / 8.76 / 46 / -1526.63619 / 0.06469 / 3.80
6TS6-7 / -1526.56679 / 0.06167 / 8.76 / 4TS6-7 / -1526.59895 / 0.06066 / 4.09
67 / -1526.66686 / 0.06188 / 8.77 / 47 / -1526.67930 / 0.06391 / 3.82
68 / -1417.08830 / 0.05510 / 8.77 / 48 / -1417.08912 / 0.05631 / 3.82
6TS8-9 / -1417.06359 / 0.05525 / 8.77 / 4TS8-9 / -1417.07741 / 0.05576 / 3.83
69 / -1417.07927 / 0.05621 / 8.76 / 49 / -1417.09027 / 0.05740 / 3.98
6TS9-9a / -1417.06742 / 0.05442 / 8.77
69a / -1417.06861 / 0.05496 / 8.77
6TS9a-10 / -1417.06676 / 0.05529 / 8.78 / 4TS9-10 / -1417.07101 / 0.05712 / 4.03
610 / -1417.08915 / 0.05843 / 8.75 / 410 / -1417.08419 / 0.05903 / 4.08
6TS9a-11 / -1417.05958 / 0.05271 / 8.77 / 4TS9-11 / -1417.05459 / 0.05231 / 4.30
611 / -1417.13547 / 0.05653 / 8.75 / 411 / -1417.12237 / 0.05645 / 3.81
6TS8-12 / -1417.02310 / 0.04834 / 8.77 / 4TS8-12 / -1417.03800 / 0.04996 / 3.87
612 / -1417.09536 / 0.05202 / 8.77 / 412 / -1417.10650 / 0.05193 / 3.86
6TS12-13 / -1417.04903 / 0.05200 / 8.77 / 4TS12-13 / -1417.06961 / 0.05283 / 3.89
613 / -1417.10909 / 0.05804 / 8.76 / 413 / -1417.12737 / 0.05782 / 3.81
614 / -1524.43670 / 0.03535 / 8.75 / 414 / -1524.46490 / 0.03593 / 3.84
6TS14-15 / -1524.41946 / 0.03259 / 8.76 / 4TS14-15 / -1524.45064 / 0.03319 / 4.23
615 / -1524.51764 / 0.03323 / 8.77 / 415 / -1524.51696 / 0.03356 / 4.30
616 / -1414.93806 / 0.02654 / 8.77 / 416 / -1414.92782 / 0.02593 / 4.47
6TS16-17 / -1414.87863 / 0.02132 / 8.76 / 4TS16-17 / -1414.87589 / 0.02297 / 3.90
617 / -1414.95787 / 0.02291 / 8.76 / 417 / -1414.94116 / 0.02472 / 3.90
6TS1a-S1 / -1418.22484 / 0.06921 / 8.83
6S1 / -1418.22608 / 0.06946 / 8.82
6TSS1-2 / -1418.22368 / 0.06835 / 8.81
6TS9a-S2 / -1417.04321 / 0.04984 / 8.77 / 4TS9-S2 / -1417.03887 / 0.05072 / 4.15
6S2 / -1417.09411 / 0.05004 / 8.77 / 4S2 / -1417.09492 / 0.051740 / 3.88
6TSS2-11 / -1417.06443 / 0.04976 / 8.76 / 4TSS2-11 / -1417.09490 / 0.05160 / 3.88
6TS11-S3 / -1417.03072 / 0.05054 / 8.77 / 4TS11-S3 / -1417.07787 / 0.05279 / 3.83
6S3 / -1417.07464 / 0.05054 / 8.76 / 4S3 / -1417.10262 / 0.05214 / 3.86
6TSS3-S4a / -1417.04585 / 0.04516 / 8.76 / 4TSS3-S4 / -1417.06504 / 0.04573 / 3.93
6S4a / -1417.06793 / 0.04574 / 8.76
6TSS4a-S4 / -1417.03164 / 0.04573 / 8.76
6S4 / -1417.10356 / 0.05162 / 8.75 / 4S4 / -1417.16382 / 0.05370 / 3.79
6TS9-13 / -1417.01644 / 0.05006 / 8.77 / 4TS9-13 / -1417.01869 / 0.05021 / 4.25
6TS9-S5 / -1417.04139 / 0.05111 / 8.76 / 4TS9-S5 / -1417.05672 / 0.05340 / 4.04
6S5 / -1417.06879 / 0.05051 / 8.77 / 4S5 / -1417.09747 / 0.05159 / 4.29
6TS12-S6 / -1417.03298 / 0.04542 / 8.76 / 4TS12-S6 / -1417.07000 / 0.04615 / 3.86
6S6 / -1417.05400 / 0.04644 / 8.76 / 4S6 / -1417.07330 / 0.04660 / 3.85
6TSS6-S7 / -1417.01747 / 0.04432 / 8.77 / 4TSS6-S7 / -1417.06431 / 0.04627 / 3.87
6S7 / -1417.07617 / 0.05210 / 8.76 / 4S7 / -1417.14400 / 0.05362 / 3.83

a Values before annihilation.

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