CO substitution in the mixed-metal clusters PhCCo2Ni(CO)6Cp and PhCCo2Mo(CO)8Cp by (Z)-Ph2PCH=CHPPh2. X-ray diffraction structures and proof of ligand bridging in ... View Full Text


Ontology type: schema:ScholarlyArticle     


Article Info

DATE

2004-12

AUTHORS

Simon G. Bott, Kaiyuan Yang, Shih-Huang Huang, Michael G. Richmond

ABSTRACT

The heterometallic tetrahedrane clusters PhCCo2Ni(CO)6Cp (1) and PhCCo2Mo(CO)8Cp (3) react with the unsaturated diphosphine ligand (Z)-Ph2PCH=CHPPh2 at elevated temperature to afford the corresponding phosphine-substituted clusters PhCCo2Ni(CO)4[(Z)-Ph2PCH=CHPPh2]Cp (2) and PhCCo2Mo(CO)6[(Z)-Ph2PCH=CHPPh2]Cp (4). Clusters 2 and 4 have been isolated by column chromatography and characterized in solution by IR and NMR (1H and 31P) spectroscopies, and the solid-state structures of these clusters have been determined by X-ray crystallography. PhCCo2Ni(CO)4[(Z)-Ph2PCH=CHPPh2]Cp crystallizes in the triclinic space group P-l, a = 10.8142(7), b = 10.8994(6), c = 17.661(2) Å, α = 82.870(6), β = 86.149(7), γ = 64.493(5)∘, V = 1864.0(2) Å3, Z = 2, Dcacl = 1.495 g/cm3; R = 0.0409, Rw = 0.0424 for 3147 observed reflections with I > 3σ(I). PhCCo2Mo(CO)6[(Z)-Ph2PCH=CHPPh2]Cp, as the hexane solvent, crystallizes in the monoclinic space group P21/c, a = 12.706(4), b = 17.367(3), c = 21.639(7) Å, β = 106.48(3)∘, V = 4579(1) Å3, Z = 4, Dcacl = 1.478 g/cm3; R = 0.0605, Rw = 0.0724 for 1330 observed reflections with I > 3σ(I). The solid-state structures of 2 and 4 confirm a bridging coordination mode for the (Z)-Ph2PCH=CHPPh2 ligand, with adjacent cobalt centers being ligated by the ancillary phosphine ligand. The structural highlights of these new mixed-metal clusters are discussed relative to the homometallic tetrahedrane cluster PhCCo3(CO)7[(Z)-Ph2PCH=CHPPh2]. More... »

PAGES

883-891

Identifiers

URI

http://scigraph.springernature.com/pub.10.1007/s10870-004-7723-3

DOI

http://dx.doi.org/10.1007/s10870-004-7723-3

DIMENSIONS

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