Bhargava S K, Mohr F, Bennett M A, Welling L L, Willis A C
Research School of Chemistry, Australian National University, Canberra, ACT 0200, Australia.
Inorg Chem. 2001 Aug 13;40(17):4271-5. doi: 10.1021/ic010272i.
The binuclear cycloaurated compounds [Au(2)(mu-C(6)H(3)-2-PPh(2)-n-Me)(2)] (n = 5, 1a; n = 6, 1b) react with the digold(I) complexes [Au(2)(mu-S(2)CN(n)()Bu(2))(2)] and Au(2)(mu-dppm)(2)(2) to give heterobridged dinuclear complexes [Au(2)(mu-C(6)H(3)-2-PPh(2)-n-Me)(mu-S(2)CN(n)Bu(2))] (n = 5, 5a; n = 6, 5b) and [Au(2)(mu-C(6)H(3)-2-PPh(2)-n-Me)(mu-dppm)]PF(6), (n = 5, 9a; n = 6, 9b), respectively. Complex 5a exists in the solid state as an infinite zigzag chain of dimeric units with intramolecular Au-Au separations of 2.8331(3) and 2.8243(3) A for independent molecules and intermolecular Au-Au separations of 3.0653(3) and 3.1304(3) A. Both 5a and 5b undergo oxidative addition with halogens to give the heterovalent, gold(I)-gold(III) compounds [XAu(I)(mu-2-Ph(2)PC(6)H(3)-n-Me)Au(III)X(eta(2)-S(2)CN(n)Bu(2))] [n = 5, X = Cl (6a), I (8a); n = 6, X = Cl (6b), Br (7b), I (8b)]. Compound 8a has been shown by X-ray crystallography to contain a gold(III) atom coordinated in a planar array by bidentate, chelating di-n-butyldithiocarbamate, iodide, and the sigma-aryl carbon atom, together with a gold(I) atom that is linearly coordinated by the phosphorus atom of the arylphosphine and by iodide. The intramolecular gold-gold distance of 3.2201(3) A indicates little or no interaction between the metal atoms. In contrast to the behavior of the homobridged complexes 1a and 1b, the heterobridged dithiocarbamate complexes 5a and 5b give structurally similar products on reaction with halogens, irrespective of the position of the ring methyl substituent. Crystal data for [Au(2)(mu-C(6)H(3)-2-PPh(2)-5-Me)(mu-S(2)CN(n)Bu(2))] (5a): triclinic, space group P1 (No. 2), with a = 11.3398(1), b = 15.9750(2), c = 16.4400(3) A, alpha = 91.0735(9), beta = 109.3130(7), gamma = 90.7666(8) degrees, V = 2809.47(6) A(3), and Z = 4. Crystal data for [IAu(I)(mu-2-Ph(2)PC(6)H(3)-5-Me)Au(III)I(eta(2)- S(2)CN(n)Bu(2))] (8a): triclinic, space group P1 (No. 2), with a = 8.6136(2), b = 9.3273, c = 21.1518(4) A, alpha = 84.008(1), beta = 84.945(1), gamma = 75.181(1) degrees, V = 1630.54(6) A(3), and Z = 2.
双核环金属化化合物[Au₂(μ-C₆H₃-2-PPh₂-n-Me)₂]（n = 5，1a；n = 6，1b）与二金（I）配合物[Au₂(μ-S₂CN(n)Bu₂)₂]和Au₂(μ-dppm)₂₂反应，分别生成杂桥联双核配合物[Au₂(μ-C₆H₃-2-PPh₂-n-Me)(μ-S₂CN(n)Bu₂)]（n = 5，5a；n = 6，5b）和[Au₂(μ-C₆H₃-2-PPh₂-n-Me)(μ-dppm)]PF₆（n = 5，9a；n = 6，9b）。配合物5a在固态下以二聚单元的无限之字形链存在，独立分子的分子内金-金间距为2.8331(3) Å和2.8243(3) Å,分子间金-金间距为3.0653(3) Å和3.1304(3) Å。5a和5b都与卤素发生氧化加成反应，生成异价的金（I）-金（III）化合物[XAu(I)(μ-2-Ph₂PC₆H₃-n-Me)Au(III)X(η²-S₂CN(n)Bu₂)] [n = 5，X = Cl (6a)，I (8a)；n = 6，X = Cl (6b)，Br (7b)，I (8b)]。X射线晶体学表明，化合物8a含有一个金（III）原子，它通过双齿螯合二正丁基二硫代氨基甲酸盐、碘化物和σ-芳基碳原子以平面排列方式配位，还有一个金（I）原子，它通过芳基膦的磷原子和碘化物以线性方式配位。分子内金-金间距为3.2201(3) Å，表明金属原子之间几乎没有相互作用。与均桥联配合物1a和1b的行为不同，杂桥联二硫代氨基甲酸盐配合物5a和5b与卤素反应生成结构相似的产物，与环甲基取代基的位置无关。[Au₂(μ-C₆H₃-2-PPh₂-5-Me)(μ-S₂CN(n)Bu₂)]（5a）的晶体数据：三斜晶系，空间群P1（编号2），a = 11.3398(1) Å，b = 15.9750(2) Å，c = 16.4400(3) Å，α = 91.0735(9)°，β = 109.3130(7)°，γ = 90.7666(8)°，V = 2809.47(6) ų，Z = 4。[IAu(I)(μ-2-Ph₂PC₆H₃-5-Me)Au(III)I(η²-S₂CN(n)Bu₂)]（8a）的晶体数据：三斜晶系，空间群P1（编号2），a = 8.6136(2) Å，b = 9.3273 Å，c = 21.1518(4) Å，α = 84.008(1)°，β = 84.945(1)°，γ = 75.181(1)°，V = 1630.54(6) ų，Z = 2。
