Chandrasekhar V, Kingsley S, Vij A, Lam K C, Rheingold A L
Department of Chemistry, Indian Institute of Technology, Kanpur-208016, India.
Inorg Chem. 2000 Jul 24;39(15):3238-42. doi: 10.1021/ic991255k.
The reaction of methylphosphine sulfide, MeP(S)(3,5-Me2Pz)2, 1, with anhydrous CuCl2 affords a tetranuclear copper cluster[Cu2Cl2(3,5-Me2Pz)3(MePO3)]2, 2, and a dinuclear compound Cu2Cl4(3,5-Me2Pz)4, 3. This reaction involves a metal-assisted desulfurization along with concomitant hydrolysis of P-N bonds. The X-ray structures of 1-3 have been determined, and the crystal parameters for these are the following. 1: space group = C2/c, a = 15.2552(1) A, b = 8.7364(2) A, c = 21.4490(3) A, beta = 93.349(1) degrees, V = 2853.74(8) A3, and Z = 8. 2: space group = P2(1)/n, a = 12.5964(4) A, b = 15.7773(4) A, c = 13.9781(4) A, beta = 116.6280(10) degrees, V = 2483.32(12) A3, and Z = 2. 3: space group = P2(1)/c, a = 8.7137(8) A, b = 13.5493(14) A, c = 11.8847(12) A, beta = 106.179(2) degrees, V = 1347.6(2) A3, and Z = 2. The structure of 2 shows that it comprises two dinuclear copper cores bridged together by two tripodal methylphosphinate, MePO3, ligands. 2 is weakly antiferromagnetically coupled, as revealed by variable temperature magnetic susceptibility measurements.
甲基硫代膦，MeP(S)(3,5-Me₂Pz)₂（1）与无水CuCl₂反应生成四核铜簇合物[Cu₂Cl₂(3,5-Me₂Pz)₃(MePO₃)]₂（2）和双核化合物Cu₂Cl₄(3,5-Me₂Pz)₄（3）。该反应涉及金属辅助脱硫以及P-N键的伴随水解。已确定了1 - 3的X射线结构，其晶体参数如下。1：空间群 = C2/c，a = 15.2552(1) Å，b = 8.7364(2) Å，c = 21.4490(3) Å，β = 93.349(1)°，V = 2853.74(8) ų，Z = 8。2：空间群 = P2(1)/n，a = 12.5964(4) Å，b = 15.7773(4) Å，c = 13.9781(4) Å，β = 116.6280(10)°，V = 2483.32(12) ų，Z = 2。3：空间群 = P2(1)/c，a = 8.7137(8) Å，b = 13.5493(14) Å，c = 11.8847(12) Å，β = 106.179(2)°，V = 1347.6(2) ų，Z = 2。2的结构表明它由两个双核铜核通过两个三脚架状甲基次膦酸酯MePO₃配体桥连在一起。变温磁化率测量表明2存在弱反铁磁耦合。
