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CUNNINGHAM, D,HIGGINS, T,MCARDLE, P,CORRIGAN, W,FOLEY, R,MANNING, AR
1994
November
Journal Of Organometallic Chemistry
THE STRUCTURE OF [(CO(ETA(4)-C6H10)(CO)(2))2SNCL2] IN THE SOLID-STATE (C6H10-2,3-DIMETHYLBUTA-1,3-DIENE)
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Optional Fields
COBALT TIN DIOLEFIN CARBONYL CRYSTAL STRUCTURE TRICARBONYL COMPLEXES BEHAVIOR
481
63
68
Reaction of [{Co(CO)(4)}(2)SnX(2)] (X = Cl, Br or I) with bicycle [2.2.1] hepta-2,5-diene, C7H8, and a variety of 1,3-dienes has allowed the isolation of [{Co(eta(4)-C7H8)(CO)(2)}{Co(CO)(4)}SnX(2)], [{Co(eta(4)-C7H8)(CO)(2)}(2)SnX(2)] and [{Co(eta(4)-C6H10)(CO)(2)}2SnCl2] only (C6H10 = 2,3-dimethylbuta-1,3-diene). An X-ray diffraction study of [{Co(eta(4)-C6H10)(CO)(2)}2SnCl2] has shown that in this complex there is distorted tetrahedral coordination about Sn arising from the different electronegativities of its substituents. The coordination about cobalt is most simply described as distorted trigonal bipyramidal (tbp) the first time that this stereochemistry has been found in a five-coordinated d(8) metal complex containing an eta(4)-(1,3-diene) ligand. The Sn occupies an axial sire, and the diene is as near to axial-equatorial as it can be. However, as a consequence of the size and shape of the diene, whereas the midpoint of its C(3)-C(4) bond lies close to the equatorial plane, that of its C(1)-C(2) bond does not lie on the Sn-Co axis. The coordination is distorted from tbp towards square-based pyramidal (sp). It is shown that rotation of the diene about an axis through its centroid and the cobalt atom leads in turn to various tbp and sp structures and distortions thereof. In all these the diene is coordinated axial-equatorial (tbp) or basal-basal (sp), but the other three ligands occupy the other coordination positions in turn.
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