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Co-ordinatively Unsaturated Diene Complexes of Tungsten(II) and their Reactions with Nucleophiles to give Six- and Seven-co-ordinate Derivatives
Davidson, Jack L.,Vasapollo, Guiseppe
, p. 2231 - 2238 (2007/10/02)
2> reacts with the 'dienes' (L') cyclo-octa-1,5-diene (cod), cyclo-octatetraene (cot), and norbornadiene (bicyclohepta-2,5-diene, nbd) to give co-ordinatively unsaturated complexes .These react with Lewis bases L t, PMe2Ph, or P(OMe)3> (1:1 molar ratio) to give co-ordinatively unsaturated diene complexes via intermediate 1:1 adducts isolated in the case of the norbornadiene complexes.With a 3:1 molar ratio of ligand:metal, displacement of cod or cot occurs to give t>, while a 4:1 molar ratio (L=CNBut) gives t)4>.In contrast, forms monocarbonyl diene complexes 2=2,2'-bipyridyl>.Proton and 31P n.m.r. studies of reveal the presence of two isomeric forms which exhibit dynamic stereochemistry at ambient temperature while the static form of one isomer could be detected at lower temperatures.
