Auracarboranes with and without Au-Au interactions: An unusually strong aurophilic interaction
Auracarboranes with and without Au-Au interactions: An unusually strong aurophilic interaction
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DOI：
10.1021/ja953976y
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发表时间：
1996-03-20
影响因子：
15
通讯作者：
Hawthorne, MF
中科院分区：
文献类型：
--
作者：
Harwell, DE;Mortimer, MD;Hawthorne, MF
合成了金碳硼烷1，2-（AuPPh（3））（2）-1，2-C2 B10 H10（1）和1，1 '-（AuPPh（3））（2）-[2-（1'，2 '-C2 B10 H10）-1，2-C2 B10 H10]（2）。这两种化合物的特征在于通过NMR和X-射线晶体学。发现化合物2含有金中心之间的亲金相互作用。变温核磁共振研究表明，分离金-金键合态和非键合态的能垒为11 +/- 1 kcal/mol。化合物1以单斜晶系空间群P2（1）/c结晶，其中a = 18.3380（9）埃，B = 14.1037（6）埃，19.4716（8）埃，β = 112.003（2）度，V = 4669埃（3），并且Z = 4。使用Mo K α辐射收集数据，最大2 θ = 50度，给出8865个独特反射，并通过重原子方法解析结构。对于3423个I > 3 sigma（I）的独立反射，最终差异指数为R = 0.047，R（w）= 0.055。化合物2以单斜晶系空间群P2（1）/c结晶，其中a = 14.058（6）埃，B = 18.365（8）埃，c = 20.387（9）埃，β = 109.22（1）度，V = 4970埃（3），并且Z = 4。使用Mo K α辐射收集数据，最大2 θ = 45度，给出5232个独特的反射，并通过重原子方法解析结构。对于I > 3 sigma（I）的2536个独立反射，最终差异指数为R = 0.066，R（w）= 0.069。
The auracarboranes 1,2-(AuPPh(3))(2)-1,2-C2B10H10 (1) and 1,1'-(AuPPh(3))(2)-[2-(1',2'-C2B10H10)-1,2-C2B10H10] (2) have been synthesized. Both compounds were characterized by NMR and X-ray crystallography. Compound 2 was found to contain an aurophilic interaction between the gold centers. A variable-temperature NMR investigation indicated that the energy barrier separating the gold-gold bonded state and the nonbonded state is 11 +/- 1 kcal/mol. Compound 1 crystallized in the monoclinic space group P2(1)/c with a = 18.3380(9) Angstrom, b = 14.1037(6) Angstrom, 19.4716(8) Angstrom, beta = 112.003(2)degrees, V = 4669 Angstrom(3), and Z = 4. Data were collected using Mo K alpha radiation, to a maximum 2 theta = 50 degrees, giving 8865 unique reflections, and the structure was solved by heavy atom methods. The final discrepancy index was R = 0.047, R(w) = 0.055 for 3423 independent reflections with I > 3 sigma(I). Compound 2 crystallized in the monoclinic space group P2(1)/c with a = 14.058(6) Angstrom, b = 18.365(8) Angstrom, c = 20.387(9) Angstrom, beta = 109.22(1)degrees, V = 4970 Angstrom(3), and Z = 4. Data were collected using Mo K alpha radiation, to a maximum 2 theta = 45 degrees, giving 5232 unique reflections, and the structure was solved by heavy atom methods. The final discrepancy index was R = 0.066, R(w) = 0.069 for 2536 independent reflections with I > 3 sigma(I).