The reaction between the half-sandwich cyclopentadienyl complexes [M(η5-C5Me5)Cl2(PEt3)] (M = Rh, Ir) and [cis-M′(C6F5)2(thf)2] (M′ = Pt, Pd; thf = tetrahydrofuran) affords the corresponding chloride-bridged heterobinuclear Rh,Ir/Pt,Pd complexes [(PEt3)(η5-C5Me5)M(μ-Cl)2M′(C6F5)2] (1−4). In contrast, similar reactions with the chloro-bridged binuclear compounds [{M(η5-C5Me5)Cl(μ-Cl)}2] (M = Rh, Ir) lead instead to the unexpected mixed salt complexes {Cp*M(μ-Cl)3MCp*}2[{(C6F5)2M′(μ-Cl)}2] (M = Rh, Ir; M′ = Pt, Pd) (5−8) as a result of chloride transfer. The structures of [(PEt3)(η5-C5Me5)Rh(μ-Cl)2Pt(C6F5)2] (1) and {Cp*Rh(μ-Cl)3RhCp*}2[{(C6F5)2Pd(μ-Cl)}2] (6) have been determined by X-ray diffraction analyses. The reactivity of the new chloride-bridged heterobinuclear compounds 1−4 towards the alkynylating agents [M′′(C≡CR)]n (M′′ = Cu, Ag) has also been investigated: a new type of tetranuclear product, [(PEt3)Cp*M(μ-1κCα:η2-C≡CPh)2M′′2(μ-4κCα:η2-C≡CPh)2Pt(C6F5)2] (M = Rh, Ir; M′′ = Cu, Ag) (9−12), was obtained, and fully characterized in the case of complex [(PEt3)Cp*Rh(μ-1κCα:η2-C≡CPh)2Cu2(μ-4κCα:η2-C≡CPh)2Pt(C6F5)2] (9).
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Ara et al. (2001) studied this question.
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