Auracarboranes with and without Au-Au Interactions: An Unusually Strong Aurophilic Interaction
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- 作者：David E. Harwell ; Mark D. Mortimer ; Carolyn B. Knobler ; Frank A. L. Anet ; and M. Frederick Hawthorne
- 刊名：Journal of the American Chemical Society
- 出版年：1996
- 出版时间：March 20, 1996
- 年：1996
- 卷：118
- 期：11
- 页码：2679 - 2685
- 全文大小：246K
- 年卷期：v.118,no.11(March 20, 1996)
- ISSN：1520-5126
文摘
The auracarboranes1,2-(AuPPh3)2-1,2-C2B10H10(1) and1,1'-(AuPPh3)2-[2-(1',2'-C2B10H10)-1,2-C2B10H10](2) have been synthesized. Both compounds werecharacterized by NMR and X-ray crystallography. Compound2was found to contain an aurophilic interaction between the goldcenters. A variable-temperature NMR investigationindicated that the energy barrier separating the gold-gold bondedstate and the nonbonded state is 11 ± 1 kcal/mol.Compound 1 crystallized in the monoclinic space groupP21/c with a =18.3380(9) Å, b = 14.1037(6) Å, c=19.4716(8) Å, 
= 112.003(2)
, V = 4669Å3, and Z = 4. Data were collected usingMo K
radiation, to a maximum2
= 50, giving 8865 unique reflections, and the structure wassolved by heavy atom methods. The final discrepancyindex was R = 0.047, Rw = 0.055for 3423 independent reflections with I >3
(I). Compound 2 crystallized inthemonoclinic space group P21/c witha = 14.058(6) Å, b = 18.365(8) Å,c = 20.387(9) Å, = 109.22(1),V = 4970Å3, and Z = 4. Data were collected usingMo K radiation, to a maximum 2 = 45, giving 5232 uniquereflections,and the structure was solved by heavy atom methods. The finaldiscrepancy index was R = 0.066, Rw= 0.069 for2536 independent reflections with I >3(I).
= 112.003(2), V = 4669Å3, and Z = 4. Data were collected usingMo K radiation, to a maximum2 = 50, giving 8865 unique reflections, and the structure wassolved by heavy atom methods. The final discrepancyindex was R = 0.047, Rw = 0.055for 3423 independent reflections with I >3(I). Compound 2 crystallized inthemonoclinic space group P21/c witha = 14.058(6) Å, b = 18.365(8) Å,c = 20.387(9) Å, = 109.22(1),V = 4970Å3, and Z = 4. Data were collected usingMo K radiation, to a maximum 2 = 45, giving 5232 uniquereflections,and the structure was solved by heavy atom methods. The finaldiscrepancy index was R = 0.066, Rw= 0.069 for2536 independent reflections with I >3(I).