@b_schwederski

Binuclear radical complexes of molybdenum and tungsten tetracarbonyls with bridging N-heterocycles and Group VA ligands. ESR evidence for a cis configuration

. Journal of Organometallic Chemistry, 262 (2): 171--178 (1984)
DOI: 10.1016/S0022-328X(00)99140-X

Abstract

The reactions of Mo(CO)6 or W(CO)6 and of bridging N-heterocyclic ligands (L) such as pyrazine or 4,4'-bipyridine with K were studied by ESR spectroscopy in the presence of excess phosphine, phosphite or arsine ligands. In many cases, double substitution at the metals could be obsd., yielding (XR3)(CO)4M-L-M(CO)4(XR3)-. (X = P, As; R = alkyl, aryl, alkoxy; M = Mo, W). ESR study of the complexes in THF soln. revealed extensive coupling of the unpaired electron with the nuclei 1H, 13C(CO), 14N, 31P, 75As, 95.97Mo and 183W. Evidence for a cis configuration at the metals is presented, and a p*/smx* hyperconjugation model is used to account for the facile substitution of CO and for the spin transfer to the peripheral nuclei. on SciFinder(R)

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