Bis(hydrosulfido)-bridged dinuclear rhodium(I) complexes as a platform for the synthesis of trinuclear sulfido aggregates with the core [MRh2(μ3-S2)] (M = Rh, Ir, Pd, Pt, Ru).

摘要: The reaction of [Rh(μ-SH)(CO)(PPh3)]2 or [Rh(μ-SH){P(OPh)3}2]2 with [Cp*MCl2]2 (M = Rh, Ir) in the presence NEt3 afforded Rh3 and IrRh2 sulfido-bridged compounds [Cp*M(μ3-S)2Rh2(CO)2(PPh3)2] 1; Ir, 2) [Cp*Rh(μ3-S)2Rh2{P(OPh)3}4] (3). [MCl2(cod)] Pd, Pt), cis-[PtCl2(PPh3)2] [(η6-C6H6)RuCl2]2 under same experimental conditions gave [(cod)M(μ3-S)2Rh2{P(OPh)3}4] 6; Pt, 7), [(cod)M(μ3-S)2Rh2(CO)2(PPh3)2] 8; 9), [(PPh3)2Pt(μ3-S)2Rh2(CO)2(PPh3)2] (10) [(η6-C6H6)Ru(μ3-S)2Rh2(CO)2(PPh3)2] (12), PdRh2, PtRh2 RuRh2 trimetallic cores. aggregates derived from were isolated as a mixture trans cis isomers which isomer predominates. 2 equiv. n-BuLi at 253 K followed by addition [Cp*IrCl2]2 [Cp*Ir(μ3-S)2Rh2{P(OPh)3}4] (4) [Cp*2ClIr2(μ3-S)2Rh{P(OPh)3}2] (5) 3 : 2 ratio. compound [(η6-C6H6)Ru(μ3-S)2Rh2{P(OPh)3}4] (11) was prepared similarly using deprotonating agent. molecular structures 3, 6, 7, 9 11 have been determined X-ray analysis. trinuclear complexes exhibit an asymmetric triangular metal core two triply bridging sulfido ligands resulting distorted trigonal-bipyramidal M3(μ3-S)2 heterometallic metal–sulfur core.