Sterenberg Brian T, Wrigley Christian T, Puddephatt Richard J
Department of Chemistry, University of Western Ontario, London, Ontario, Canada N6A 5B7.
Dalton Trans. 2015 Mar 28;44(12):5555-68. doi: 10.1039/c4dt03966a.
The chemistry of the heterobinuclear platinum-iridium complex [PtIr(CO)3(μ-dppm)2][PF6], 1, dppm = Ph2PCH2PPh2, is described. The reaction of a hydride with 1 gave [HPtIr(CO)2(μ-dppm)2], by displacement of the carbonyl ligand from platinum, while reaction of 1 with dihydrogen, hydrogen chloride or Ph2MeSiH gave the fluxional complex [PtIrH4(CO)(μ-dppm)2][PF6], [PtIrH2Cl2(CO)(μ-dppm)2][PF6], or [PtIrH(SiMePh2)(CO)2(μ-dppm)2][PF6], respectively, by oxidative addition at iridium. Complex 1 reacted, often regioselectively, with several alkynes to give the μ-η(1),η(1) bridging alkyne complexes [PtIr(μ-RCCR')(CO)2(μ-dppm)2][PF6], R = H, R' = Ph, 4-C6H4Me, CO2Me; R = Ph, R' = CO2Me; R = R' = CO2Me. The complex [PtIr(μ-HCC-4-C6H4Me)(CO)2(μ-dppm)2][PF6] reacted reversibly with CO to give [PtIr(μ-HCC-4-C6H4Me)(CO)3(μ-dppm)2][PF6] and [PtIr(CO)3(μ-dppm)2][PF6], 1. With HCl, [PtIr(μ-HCC-4-C6H4Me)(CO)2(μ-dppm)2][PF6] reacted to give [PtIrHCl(μ-HCC-4-C6H4Me)(CO)2(μ-dppm)2][PF6], by oxidative addition at iridium, and then the alkenylplatinum derivative [PtIrCl{HC=CH(4-C6H4Me)}(CO)2(μ-dppm)2][PF6]. [PtIr(μ-HCC-4-C6H4Me)(CO)2(μ-dppm)2][PF6] reacted slowly with dihydrogen to give 4-MeC6H4CH=CH2 and [PtIrH4(CO)(μ-dppm)2][PF6]. The complex [PtIr(μ-HCCPh)(CO)2(μ-dppm)2][PF6] is intensely luminescent in solution at room temperature, with features characteristic of a d(8)-d(8) face-to-face complex.
描述了异双核铂 - 铱配合物[PtIr(CO)3(μ - dppm)2][PF6]（1，dppm = Ph2PCH2PPh2）的化学性质。氢化物与1反应，通过从铂上取代羰基配体得到[HPtIr(CO)2(μ - dppm)2]，而1与氢气、氯化氢或Ph2MeSiH反应，通过铱上的氧化加成分别得到通量配合物[PtIrH4(CO)(μ - dppm)2][PF6]、[PtIrH2Cl2(CO)(μ - dppm)2][PF6]或[PtIrH(SiMePh2)(CO)2(μ - dppm)2][PF6]。配合物1通常具有区域选择性地与几种炔烃反应，生成μ - η(1),η(1)桥连炔烃配合物[PtIr(μ - RCCR')(CO)2(μ - dppm)2][PF6]，其中R = H，R' = Ph、4 - C6H4Me、CO2Me；R = Ph，R' = CO2Me；R = R' = CO2Me。配合物[PtIr(μ - HCC - 4 - C6H4Me)(CO)2(μ - dppm)2][PF6]与CO可逆反应，生成[PtIr(μ - HCC - 4 - C6H4Me)(CO)3(μ - dppm)2][PF6]和[PtIr(CO)3(μ - dppm)2][PF6]（1）。与HCl反应时，[PtIr(μ - HCC - 4 - C6H4Me)(CO)2(μ - dppm)2][PF6]通过铱上的氧化加成反应生成[PtIrHCl(μ - HCC - 4 - C6H4Me)(CO)2(μ - dppm)2][PF6]，然后生成烯基铂衍生物[PtIrCl{HC=CH(4 - C6H4Me)}(CO)2(μ - dppm)2][PF6]。[PtIr(μ - HCC - 4 - C6H4Me)(CO)2(μ - dppm)2][PF6]与氢气缓慢反应，生成4 - MeC6H4CH=CH2和[PtIrH4(CO)(μ - dppm)2][PF6]。配合物[PtIr(μ - HCCPh)(CO)2(μ - dppm)2][PF6]在室温下的溶液中强烈发光，具有d(8)-d(8)面对面配合物的特征。
