COMPLEXES OF 2-DIPHENYLPHOSPHINOBENZENETHIOL AND 2-DIPHENYLPHOSPHINO-6-TRIMETHYLSILYLBENZENETHIOL WITH RHODIUM AND IRIDIUM - CRYSTAL AND MOLECULAR-STRUCTURES OF [IRCL2(PH2PC6H4S)(PMEPH(2))(2)] AND [IR(PH2PC6H4S)3].0.75CH(2)CL(2)

被引:19
作者
DILWORTH, JR
LU, CZ
MILLER, JR
ZHENG, YF
机构
来源
JOURNAL OF THE CHEMICAL SOCIETY-DALTON TRANSACTIONS | 1995年 / 12期
关键词
D O I
10.1039/dt9950001957
中图分类号
O61 [无机化学];
学科分类号
070301 ; 081704 ;
摘要
The reaction between [IrCl3(PMePh(2))(3)] and 2-diphenylphosphinobenzenethiolate in methanol yielded only [IrCl2(Ph(2)PC(6)H(4)S)(PMePh(2))(2)] 1 whereas, with IrCl3, [Ir(Ph(2)PC(6)H(4)S)(3)] 2 was formed. The crystal structures of 1 and 2 have been determined. They reveal octahedral geometries about Ir with a mer arrangement of P donors in both cases. A similar reaction using [RhCl(PPh(3))(3)] as precursor gave an analogous rhodium complex which exists as a mixture of isomers in solution with mer and fac P donors. However, with the sterically demanding 2-Ph(2)P(6-Me(3)Si)C6H3SH the complexes [M{Ph(2)P(Me(3)Si)C6H3S}(3)] (M = Rh or Ir) were generated. Their P-31 NMR spectra indicate that these are single species with different structures from those of the Ph(2)PC(6)H(4)S complexes. The reaction between [IrCl(CO)(PPh(3))(2)] and the two thiols (HL) yielded the hydride complexes [IrH(CO)L(2)] the H-1 and P-31 NMR and IR spectra of which confirmed the presence of the hydride ligand and trans-P atoms. The Ph(2)PC(6)H(4)S complex isomerises slowly in the solid state and in solution to a species with cis-P atoms.
引用
收藏
页码:1957 / 1964
页数:8
相关论文
共 17 条