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Binuclear platinum-iridium complexes: synthesis, reactivity and luminescence.
Sterenberg, Brian T; Wrigley, Christian T; Puddephatt, Richard J.
Afiliación
  • Sterenberg BT; Department of Chemistry, University of Western Ontario, London, Ontario, Canada N6A 5B7. pudd@uwo.ca.
Dalton Trans ; 44(12): 5555-68, 2015 Mar 28.
Article en En | MEDLINE | ID: mdl-25697241
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.

Texto completo: 1 Colección: 01-internacional Base de datos: MEDLINE Idioma: En Revista: Dalton Trans Asunto de la revista: QUIMICA Año: 2015 Tipo del documento: Article Pais de publicación: Reino Unido

Texto completo: 1 Colección: 01-internacional Base de datos: MEDLINE Idioma: En Revista: Dalton Trans Asunto de la revista: QUIMICA Año: 2015 Tipo del documento: Article Pais de publicación: Reino Unido