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Organisch-Chemisches

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Organisch-Chemisches

This journal is ? The Royal Society of Chemistry 1999

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    Theoretical study on linear dicyanide and dicarbonyl complexes of the metals Au, Hg,

    3+and Tl: On the possible existence of a [Tl(CO)] cation2

Volker Jonas and Walter Thiel*

    Organisch-Chemisches Institut, Universität Zürich, Winterthurerstrasse 190, CH-8057 Zürich, Switzerland

Supplementary Material

Tables S1 S8

This journal is ? The Royal Society of Chemistry 1999

    -+Table S1 Experimental and Calculated Bond Lengths (in Å) for [Au(CN)], [Hg(CN)], [Tl(CN)], 222

    +2+3+[Au(CO)], [Hg(CO)], and [Tl(CO)] 222__________________________________________________________________________________

    -+ [Au(CN)] [Hg(CN)] [Tl(CN)] 222________________________________________________

     Au-C C-N Hg-C C-N Tl-C C-N

    __________________________________________________________________________________

    aadde exp. 2.019(12) 1.106(14) 2.015(3) 1.137(3)

    bb 1.979(12) 1.167(16)

    cc 1.982(19) 1.123(27)

     BP86/ECP1 1.996 1.183 2.019 1.177 2.047 1.179

     MP2/ECP1 1.999 1.189 2.017 1.185 2.027 1.190

     CCSD(T)/ECP1 2.019 1.182 2.031 1.177 2.042 1.180

    __________________________________________________________________________________

__________________________________________________________________________________

    +2+3+ [Au(CO)] [Hg(CO)] [Tl(CO)] 222________________________________________________

     Au-C C-O Hg-C C-O Tl-C C-O

    __________________________________________________________________________________

    ff exp. 2.083(10) 1.104(12)

     BP86/ECP1 1.988 1.139 2.116 1.131 2.257 1.132

     MP2/ECP1 2.030 1.136 2.148 1.131 2.232 1.132

     CCSD(T)/ECP1 2.016 1.122 2.130 1.116 2.203 1.117

    __________________________________________________________________________________

    a12 Reference 45a, average values for [LysineH][Au(CN)]. Specific values: Au-C 2.022(12) Å, Au-C 2

    11222.015(12) Å; C-N 1.100(14) Å, C-N 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{(PhPCH)AsPh}][Au(CN)]. 22222

    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)(OH)] in aqueous solution, obtained 224

    from large-angle X-ray scattering.

    f Reference 5b, values for [Hg(CO)][SbF]. 22112

    This journal is ? The Royal Society of Chemistry 1999

    -1-+Table S2 Vibrational Frequencies (in cm) for [Au(CN)], [Hg(CN)] and [Tl(CN)] 222__________________________________________________________________________________

    a,b,c Exp. BP86 ;, MP2 ;, CCSD(T) ;, i

     (solution) ECP1 ECP1 ECP1

    __________________________________________________________________________________

    - [Au(CN)] 2

    +0 2103 -58 2189 +28 [CN] 2161 2161 g1

    + [MC] 446 432 -14 430 -16 414 -32 g2

    + [CN] 2142 2145 + 3 2091 -51 2176 +24 u3

    + [MC] 426 412 -14 409 -17 395 -31 u4

     [MCN] 301 276 -25 264 -37 260 -41 g5

     [MCN] 410 417 + 7 388 -22 377 -33 u6

     [CMC] 125 77 -48 77 -48 76 -49 u7__________________________________________________________________________________

     [Hg(CN)] 2

    + [CN] 2197 2212 +15 2126 -71 2226 +29 g1

    + [MC] 412 419 + 7 436 +24 426 +14 g2

    + [CN] 2197 2212 +15 2123 -74 2223 +26 u3

    + [MC] 442 454 +12 467 +25 457 +15 u4

     [MCN] 276 238 -38 224 -52 223 -53 g5

     [MCN] 341 349 + 8 330 -11 325 -16 u6

     [CMC] 75 73 72 u7__________________________________________________________________________________

    + [Tl(CN)] 2

    + [CN] 2187 2192 + 5 2083 -103 2200 +13 g1

    + [MC] 390 384 - 6 432 +42 417 +27 g2

    + [CN] 2199 2198 - 1 2084 -115 2201 + 2 u3

    +d [MC] 345 472 500 487 u4

     [MCN] 207 184 180 g5

     [MCN] 300 278 273 u6

     [CMC] 67 66 64 u7__________________________________________________________________________________

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

    data from aqueous solution.

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

    aqueous solution.

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

    +[Tl(CN)(OH)]. 224

    d Assignment inconsistent with present theoretical results.

    This journal is ? The Royal Society of Chemistry 1999

    -1+2+3+Table S3 Vibrational Frequ