D. A. Pogrebnyakov

Chemistry of vinylidene complexes. XIII. The reaction between Cp(CO)2MnPt(μ-CCHPh)(η2-dppm) and Fe2(CO)9: simultaneous formation of the μ3-vinylidene MnFePt and μ4-vinylidene PtFe3 clusters. Crystal structure of (η5-C5H5)MnFePt(μ3-CCHPh)(CO)6[η1-Ph2PCH2P(O)Ph2] ☆ ☆☆

Abstract The reaction between [Cp(CO)2MnPt(μ-CCHPh)(η2-dppm)] 2 (1) and [Fe2(CO)9] gives heterometallic MnFePt and PtFe3 vinylidene clusters 2–4, in which diphosphine ligands are coordinated to metal cores in three different modes. In [(η2-dppm)PtFe3(μ4-CCHPh)(CO)9] (2) the Pt atom is chelated by dppm while in [CpMnFePt(μ3-CCHPh)(μ-dppm)(CO)5] (3) dppm bridges the Pt–Fe bond. Complex 3 was shown to exist in two isomeric forms. The novel complex {CpMnFePt(μ3-CCHPh)(CO)6[η1-Ph2PCH2P(O)Ph2]} (4), characterized by X-ray diffraction study, possesses a trimetallic chain core. The diphosphine ligand in 4 links to platinum by only one of phosphorus atoms whereas the second P atom is uncoordinated and oxidized to the phosphineoxide group.

Chemistry of vinylidene complexes: 15. Transmetallation of μ-vinylidene MnPd complexes. Synthesis, X-ray diffraction analysis, and mass spectrometric study of the (η5-C5H5)MnFe2(μ3-C=CHPh)(CO)8 clustercluster

The reaction of Cp(CO)2Mn=C=CHPh(1) with Pd(PPh3)4 followed by the replacement of the PPh3 ligands by diphosphines Ph2P(CH2)2PPh2 (dppe) or Ph2P(CH2)3PPh2 (dppp) (where dppe is bis(diphenylphosphino)ethane and dppp is 1,3-bis(diphenylphosphino)propane) afforded the binuclear complexes Cp(CO)2MnPd(μ-C=CHPh)(dppe) (2a) and Cp(CO)2MnPd(μ-C=CHPh)(dppp) (2b), respectively. The reactions of2a and2b with Fe2(CO)9 gave the trinuclear complex CpMnFe2(μ3-C=CHPh(CO)3 (3). Competitive transmetallation took the second pathway to yield clusters containing the PdFe3 and PdFe2 cores. Complex3 was also formed in the thermal reaction of compound1 with Fe2(CO)9. Complex3 was studied by IR spectroscopy,1H and13C NMR spectroscopy, mass-spectrometry, and X-ray diffraction analysis.

Molecular structure of a new palladium-containing vinylidene cluster [η2-Ph2P(CH2)3PPh2]PdFe3(μ4-C=CHPh)(CO)9

The structure of the vinylidene cluster [η2-Ph2P(CH2)3PPh2]PdFe3(μ4-C=CHPh)(CO)9 was established by X-ray diffraction analysis. The metal core of the molecule has a butterfly shape with the Pd atom occupying a wingtip position. The C(1)=C(2)HPh ligand is σ-bound to three atoms of the Fe2Pd triangle through the C(1) atom and is η2-coordinated to the Fe atom located in the second wingtip position via the C(1)=C(2) double bond. The Pd atom is chelated by the diphosphine ligand.

Electrochemical study of heteronuclear complex [Cp(CO)2MnCu(μ-C=CHPh)(μ-Cl)]2

The electrochemical behavior of the heteronuclear dimeric vinylidene complex [Cp(CO)2MnCu(μ-C=CHPh)(μ-Cl)]2 (I) is studied using polarography, cyclic voltammetry, and controlled-potential electrolysis on mercury and platinum electrodes in acetonitrile. The dimer is reduced in two two-electron stages: at the first stage, metal-halogen bonds are broken and binuclear monomers [Cp(CO)2MnCu(μ-C=CHPh)(Cl)]− are formed; at the second stage, mononuclear manganese complexes Cp(CO)2Mn=C=CHPh, metallic copper, and chloride ions are formed. The two-electron oxidation of dimer [Cp(CO)2MnCu(μ-C=CHPh)(μ-Cl)]2 also results in the formation of binuclear monomers, which decompose to complex Cp(CO)2Mn=C=CHPh, Cu2+ ions, and Cl− ions.