
Journal of the Chemical Society, Dalton Transactions p. 3995 - 4002 (1996)
Update date:2022-08-05
Topics:
Baker, Paul K.
Coles, Simon J.
Hibbs, David E.
Meehan, Margaret M.
Hursthouse, Michael B.
Equimolar quantities of [WI2(CO)(NCMe)(η2-RC2R′)2] (R = R′ = Me or Ph; R = Me, R′ = Ph) and PhP(CH2CH2PPh2)2 (L) reacted in CH2Cl2 at room temperature to give the mono(alkyne) complexes [WI2(CO)(L-P,P′)(η2-RC2R′)] in high yield. The molecular structures of [WI2(CO)(L-P,P′)(η2-MeC2R)] (R = Me or Ph) have been crystallographically determined. There are two independent molecules in the asymmetric unit which are diastereoisomers. The co-ordination pattern about the metal atom in [WI2(CO)-(L-P,P′)(η2-MeC 2Me)]·0.75CH2Cl2 1 is a distorted octahedron with two adjacent phosphorus atoms of the triphosphine, a carbonyl and an iodide ligand in the equatorial plane and an iodide and the but-2-yne ligand occupying axial sites. The complex [WI2(CO)(L-P,P′)(η2-MeC2Ph)] is also a distorted octahedron, with identical co-ordination to that of 1, except in that the but-2-yne ligand is substituted by the I-phenylprop-1-yne ligand. In 1 there is a pendant arm of the triphosphine ligand free to co-ordinate with other species. The reactions of the complexes [WI2(CO)(L-P,P′)(η2-RC2R)] (R = Me or Ph) as monodentate phosphine ligands with the molybdenum(II) and tungsten(II) complexes [MI2(CO)3(NCMe)2], [MI2(CO)3(NCMe)L′] (L′ = PPh3, AsPh3 or SbPh3), [MoCl(GeCl3)(CO)2(NCMe)2(PPh3)] and [WI2(CO)(NCMe)(η2-RC2R)2] (R = Me or Ph) were found to give a range of bi- and tri-metallic complexes which have all been characterised.
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