DOC

Organisch-Chemisches

By Lorraine Lewis,2014-08-04 10:29
15 views 0
Organisch-Chemisches

This journal is ? The Royal Society of Chemistry 1999

    刚刚好够好看好看更快更好看个好看过后

    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 Frequencies (in cm) for [Au(CO)], [Hg(CO)] and [Tl(CO)] 222__________________________________________________________________________________

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

     (solid) ECP1 ECP1 ECP1

    __________________________________________________________________________________

    + [Au(CO)] 2

    + [CO] 2254 2232 -22 2201 -53 2268 +14 g1

    + [MC] 400 403 + 3 374 -26 355 - 45 g2

    + [CO] 2217 2192 -25 2176 -41 2242 +25 u3

    + [MC] 354 353 - 1 325 -29 313 - 41 u4

     [MCO] 312 298 -14 299 -13 292 - 20 g5

    [MCO] 406 399 - 7 390 -16 379 - 27 u6

     [CMC] 105 60 -45 65 -40 64 - 41 u7

    __________________________________________________________________________________

    2+ [Hg(CO)] 2

    + [CO] 2281 2280 - 1 2195 -86 2296 +15 g1

    + [MC] 315 317 304 g2

    + [CO] 2278 2276 - 2 2197 -81 2295 +17 u3

    + [MC] 348 357 346 u4

     [MCO] 285 286 282 g5

     [MCO] 335 347 +12 339 + 4 331 - 4 u6

     [CMC] 65 64 62 u7

    __________________________________________________________________________________

    3+ [Tl(CO)] 2

    + [CO] 2254 2112 2264 g1

    + [MC] 245 315 290 g2

    + [CO] 2256 2115 2265 u3

    + [MC] 321 374 350 u4

     [MCO] 278 283 278 g5

     [MCO] 316 322 314 u6

     [CMC] 59 63 60 u7

    __________________________________________________________________________________

    a Reference 10b; values for solid [Au(CO)][SbF]. 2211

    b Reference 5b; values for solid [Hg(CO)][SbF]. 22112

This journal is ? The Royal Society of Chemistry 1999

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

    ++2+3+ a[Hg(CN)], [Tl(CN)], [Au(CO)], [Hg(CO)], and [Tl(CO)] 22222__________________________________________________________________________________

    bc exp. BP86 MP2 CCSD(T) exp. BP86 MP2 CCSD(T)

    ________________________________________________

    -+ [Au(CN)] [Au(CO)] 22______________________________________________________

    + [CX] s 50.1 5.6 14.6 s 475.8 191.3 272.8 u3

    + [MC] m 14.4 13.5 19.0 w 47.6 44.4 33.1 u4

     [MCX] sh 0.5 0.0 0.3 m 10.4 6.3 11.1 u6

     [CMC] m,bd 28.5 29.7 30.9 vw 0.6 0.7 0.5 u7

    __________________________________________________________________________________

    2+ [Hg(CN)] [Hg(CO)] 22_____________________________________________________

    + [CX] vs 52.4 90.5 64.5 m 13.4 14.3 1.0 u3

    + [MC] s 40.4 43.6 46.2 0.5 0.2 0.3 u4

     [MCX] m 0.3 1.5 1.4 m 18.8 9.2 13.7 u6

     [CMC] 19.7 23.9 24.0 3.3 2.5 1.9 u7

    __________________________________________________________________________________

    +3+ [Tl(CN)] [Tl(CO)] 22_____________________________________________________

    + [CX] 289.3 326.6 304.7 24.0 161.7 33.0 u3

    + [MC] 23.9 31.7 31.1 3.8 0.1 0.7 u4

     [MCX] 2.9 4.8 6.0 24.3 11.7 17.9 u6

     [CMC] 8.1 13.2 12.1 8.5 5.7 4.9 u7

    __________________________________________________________________________________ a All calculated data were obtained from the ECP1 calculations; X = O or N, respectively. b- Reference 24 for [Au(CN)]; Reference 26 for [Hg(CN)]. 22

    c+2+ Reference 10b for [Au(CO)]; Reference 5b for [Hg(CO)]. 22

This journal is ? The Royal Society of Chemistry 1999

    4-Table S5 Experimental Relative and Calculated Raman Intensities (in Å/amu) for [Au(CN)], 2

    ++2+3+ a[Hg(CN)], [Tl(CN)], [Au(CO)], [Hg(CO)], and [Tl(CO)] 22222__________________________________________________________________________________

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

    bb exp. calc. exp. calc. calc.

    __________________________________________________________________________________

    + [CN] 35 518.5 13.7 271.9 110.8 g1

    + [MC] 0.8 1.7 3.6 19.7 98.5 g2

     [MCN] 6 11.2 5.8 5.5 10.1 g5

    __________________________________________________________________________________

    __________________________________________________________________________________

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

    cd exp. calc. exp. calc. calc.

    __________________________________________________________________________________

    + [CO] vs 228.0 s 86.3 45.3 g1

    + [MC] vw 2.2 8.8 77.7 g2

     [MCO] sh 0.5 1.3 0.5 g5

    __________________________________________________________________________________ a All data at BP86/ECP2.

    b Reference 26b; peak intensities at maximum for a 1 molar aqueous solution. c Reference 10b; is weak in HSOF solution. 53

    d Reference 5b; due to overlap with the counterion bands and were not assigned. 25

This journal is ? The Royal Society of Chemistry 1999

    -1-Table S6 Experimental and Calculated Isotopic Shifts (in cm) for [Au(CN)], [Hg(CN)], 22

    ++2+3+ a[Tl(CN)], [Au(CO)], [Hg(CO)], and [Tl(CO)] 2222__________________________________________________________________________________

    bbcc Exp. ;I Calc.;I Exp. ;I Calc.;I Exp. ;I Calc.;I Exp. ;I Calc.;I

    13141314121512151316131612181218 CN CN CN CN CO CO CO CO

    _____________________________________________________________

    -+ [Au(CN)] [Au(CO)] 22__________________________________________________________________________________ + [CX] 48.4 48.5 30.4 30.4 51.5 52.9 49 49.5 g1

    + [MC] 7.3 8.5 6.5 6.5 10 14.6 g2

    + [CX] 46.4 47.1 30.4 31.0 50.5 50.1 52 51.2 u3

    + [MC] 5.6 6.4 4.5 4.7 9 9.8 u4

     [MCX] 8.2 2.4 9.0 8.9 3.5 3.9 g5

     [MCX] 13.8 1.5 14 13.1 3 2.9 u6

     [CMC] 0.1 2.0 0 0.1 5 2.5 u7__________________________________________________________________________________

    2+ [Hg(CN)] [Hg(CO)] 22__________________________________________________________________________________ [CX] 49.1 49.9 30.9 30.9 53 53.2 52.0 g1

     [MC] 7.2 8.4 5.2 11.3 g2

     [CX] 48.2 49.7 30.6 31.1 53 52.8 52.1 u3

     [MC] 6.1 7.3 4.5 9.8 u4

     [MCX] 6.8 2.0 8.3 3.8 g5

     [MCX] 11.7 1.1 10 11.1 2.7 u6

     [CMC] 0.2 2.0 0.2 2.7 u7__________________________________________________________________________________

    +3+ [Tl(CN)] [Tl(CO)] 22__________________________________________________________________________________ [CX] 49.4 30.9 52.1 52.3 g1

     [MC] 6.7 7.8 4.2 8.9 g2

     [CX] 50.0 30.5 52.4 51.9 u3

     [MC] 6.2 7.8 4.2 9.1 u4

     [MCX] 5.6 1.7 8.0 3.9 g5

     [MCX] 10.0 0.8 9.9 2.9 u6

     [CMC] 0.1 1.8 0.3 2.5 u7__________________________________________________________________________________ a12141216 Shifts relative to CN and CO, respectively. X = O or N, respectively. Calculated values at BP86/ECP2.

    b- References 23, 25 for [Au(CN)]. References 23, 27 for [Hg(CN)]. 22

    c References 10b and 5b, values for solid [Au(CO)][SbF] and [Hg(CO)][SbF]. 221122112

This journal is ? The Royal Society of Chemistry 1999

    -+ aTABLE S7 Harmonic Symmetry Force Constants F for [Au(CN)], [Hg(CN)], and [Tl(CN)] ij222______________________________________________________________________________________________________________________________

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

    bcd exp. BP86 MP2 CCSD(T) exp. BP86 MP2 CCSD(T) BP86 MP2 CCSD(T)

    ______________________________________________________________________________________________________________________________

    F 17.67 ? 17.04 16.04 17.36 18.07 ? 0.2 17.73 16.22 17.81 17.42 15.49 17.39 1,1

    0.18

    F 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 1,2

    F 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 2,2

    F 17.61 ? 17.00 16.04 17.32 18.07 ? 0.2 17.75 16.25 17.82 17.44 15.52 17.39 3,3

    0.18

    F 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 3,4

    F 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 4,4

    F 0.23 0.25 0.25 0.16 0.17 0.16 0.11 0.11 0.11 5,5

    F 0.26 0.28 0.27 0.17 0.17 0.17 0.12 0.12 0.11 6,6

    F -0.14 -0.13 -0.12 -0.08 -0.07 -0.07 -0.06 -0.06 -0.05 6,7

    F 0.56 0.47 0.45 0.52 0.43 0.41 0.43 0.42 0.39 7,7______________________________________________________________________________________________________________________________

    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.

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

    d-1-1 Reference 28c gives empirical values of 17.62 mdyn Å for F and 2.34 mdyn Å for F. 1,12,2

This journal is ? The Royal Society of Chemistry 1999

    +2+3+ TABLE S8 Harmonic Symmetry Force Constants F for [Au(CO)], [Hg(CO)], and [Tl(CO)]ij222

    a

    ______________________________________________________________________________________________________________________________

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

    b exp. BP86 MP2 CCSD(T) exp. BP86 MP2 CCSD(T) BP86 MP2 CCSD(T)

    ______________________________________________________________________________________________________________________________

    F 20.25 ? 0.1 19.51 19.16 20.26 20.49 19.14 20.77 20.16 17.85 20.33 1,1

    F 0.45 ? 0.2 0.20 0.14 0.06 -0.06 -0.03 -0.11 -0.16 0.00 -0.10 1,2

    F 2.70 ? 0.03 2.80 2.72 2.44 1.74 1.89 1.75 1.09 1.83 1.59 2,2

    F 19.95 ? 0.1 19.42 19.16 20.21 20.49 19.19 20.77 20.17 17.91 20.33 3,3

    F 0.45 ? 0.2 0.41 0.27 0.20 -0.02 -0.02 -0.09 -0.08 0.05 -0.06 3,4

    F 1.62 ? 0.03 1.67 1.54 1.42 1.62 1.75 1.62 1.43 1.94 1.72 4,4

    F 0.253 ? 0.25 0.28 0.27 0.22 0.24 0.23 0.22 0.24 0.23 5,5

    0.02

    F 0.283 ? 0.28 0.31 0.29 0.23 0.25 0.24 0.22 0.25 0.24 6,6

    0.02

    F -0.02 ? 0.02 -0.12 -0.12 -0.11 -0.06 -0.05 -0.04 -0.03 -0.03 -0.03 6,7

    F 0.77 ? 0.09 0.31 0.25 0.24 0.32 0.23 0.22 0.26 0.25 0.23 7,7______________________________________________________________________________________________________________________________

    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.

This journal is ? The Royal Society of Chemistry 1999

Report this document

For any questions or suggestions please email
cust-service@docsford.com