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Issue 12, 2015
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Binuclear platinum–iridium complexes: synthesis, reactivity and luminescence

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Abstract

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–η11 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[double bond, length as m-dash]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[double bond, length as m-dash]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 d8–d8 face-to-face complex.

Graphical abstract: Binuclear platinum–iridium complexes: synthesis, reactivity and luminescence

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Publication details

The article was received on 23 Dec 2014, accepted on 09 Feb 2015 and first published on 09 Feb 2015


Article type: Paper
DOI: 10.1039/C4DT03966A
Citation: Dalton Trans., 2015,44, 5555-5568
  • Open access: Creative Commons BY license
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    Binuclear platinum–iridium complexes: synthesis, reactivity and luminescence

    B. T. Sterenberg, C. T. Wrigley and R. J. Puddephatt, Dalton Trans., 2015, 44, 5555
    DOI: 10.1039/C4DT03966A

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