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Structural features of the CoC bond in alkylcobaloximes. The x-ray structure of trans-bis(dimethylglyoximato) (vinyl)-(pyridine)cobalt(III)

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Abstract

The X-ray crystal structural analysis of the title compound has shown that the vinyl group is σ-bonded to the cobalt atom. The CoC distance of 1.966(6) Å is shorter than that in the analogous methyl derivative mainly because of the different carbon σ-covalent radii. The CoN bond length of 2.073(3) Å is indicative of a strong trans-influence of the vinyl group, comparable with that of the methyl group. The Co atom lies 0.04 Å out of the plane of the four N-donors, being displaced towards the Py molecule. The two DH units are slightly bent (6.3°) away from the pyridine ligand.

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Cited by (11)

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    2000, Coordination Chemistry Reviews
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    The data in Table 3 demonstrate that the strong σ-donor properties of these groups lead to considerably larger STEs than those caused by CO (30, 31, 34), Cl− (32), OH− (35) or SbPh3 (36, 37). X-ray crystal structures of the cobaloximes trans-CoIIIX(dmgH)2py (27, L=py) yield CoN(py) bond distances of 2.073(3) Å for X=CHCH2− [74] and 2.028(2) Å for X=cis-CClC(H)Cl− [75], giving a difference of ca. 0.05 Å. The η1-1,2-dichlorovinyl ligand hence exerts a rather weaker STE than its unsubstituted counterpart, which can be ascribed to a decrease in basicity caused by the electronegative chlorine atoms.

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