Synthesis and Reactivity of σ-Alkynyl/P-Bonded Phosphinoalkyne Platinum Complexes toward cis-[M(C6F5)2(thf)2] (M = Pt, Pd)†

The synthesis and reactivity toward cis-[Pt(C6F5)2(THF)2] of several alkynylphosphine d8 complexes, [Pt(C6F5)(PPh2C⋮CPh)3](CF3SO3), 1, [M(COD)(PPh2C⋮CPh)2](ClO4) (M = Rh, 2, and Ir, 3), and [Pt(o-C6H4E2)(PPh2C⋮CPh)2] (E = O, 6, and S, 7), are reported. Whereas 1 gives rise to the diinserted product 8, which evolves in solution to the bis(diphenylphosphine)naphthalene-based mononuclear complex 9, analogous reactions with 2 or 3 give mixtures of products. The reactions with 6 or 7 afford binuclear heterobridged (μ-κE-o-C6H4E2)/(μ-κP:η2-PPh2C⋮CPh) 11 and 12 or trinuclear (μ3-κ2EE‘-o-C6H4E2)/(μ-κP:η2-PPh2C⋮CPh)2 13 and 14 complexes.

Alkynyldiphenylphosphine d8 (Pt, Rh, Ir) complexes: contrasting behavior toward cis-[Pt(C6F5)2(THF)2].

Diphenyl(phenylethynyl)phosphine d6 [Rh(III), Ir(III), Ru(II)] Complexes: Preparation of Homo (μ-Cl)2 and Hetero (μ-Cl)(μ-PPh2C⋮CPh) Bridged d6−d8 Compounds

Reactions between the diphenylacetylenephosphine complexes cis-[M′Cl2(PPh2CCR)2](M′= Pt or Pd, R = Ph or But) and cis-[M(C6F5)2(thf)2](M = Pt or Pd; thf = tetrahydrofuran) in a 1 : 1 molar ratio have been studied. Three types of products have been obtained: (a) asymmetric homo- and hetero-dinuclear complexes gem-[(C6F5)2M(µ-Cl)2M′(PPh2CCR)2], (b) symmetric trans-palladium derivatives [{Pd(µ-Cl)(C6F5)(PPh2CCR)}2] and (c) the unusual chloride and diphenyl (phenylethynyl) phosphine bridged dinuclear compounds [(C6F5)2Pt(µ-Cl)(µ-PPh2CCPh)M′Cl(PPh2CCPh)]. The complexes have been characterised by microanalysis, IR and NMR spectroscopy and the molecular structure of [(C6F5)2Pt(µ-Cl)(µ-PPh2CCPh)PtCl(PPh2CCPh)]·OC4H8. The NMR spectral data (1H, 19F and 31P) indicate that, in solution, mixtures of isomers [(C6F5)2Pt(µ-Cl)2M′(PPh2CCR)2] and [(C6F5)2Pt(µ-Cl)-(µ-PPh2CCPh)M′Cl(PPh2CCPh)] are present.

Homo- and hetero-dinuclear complexes of palladium and platinum containing phosphinoacetylene and/or chloride as bridging ligands

Reactivity of unsaturated clusters. Phosphoruscarbon bond activation, hydrogen migration and acetylene interconversion in the reactions of 46-electron (H)Ru3(CO)9(μ-PPh2) with Ph2PCCR (R = Ph, But, Pri). X-ray structure of Ru3(CO)9(μ-PPh2)2(μ3-η2-HCCPh): a new type of 5-vertex, 7-skeletal pair cluster

Coordination complexes of acetylenic phosphines and diphosphines

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Coordination complexes of acetylenic phosphines and diphosphines