Syntheses and characterization of phenyldiazenido and mixed phenyldiazenido–isocyanide complexes of rhenium. Crystal structure of [ReBr2(NNPh)2(PPh3)2]
Abstract
The complex [ReBr2(NNPh)2(PPh3)2]Br 1, prepared by bromination of [ReCl(NNPh)2(PPh3)2], was reduced, in thf or acetone, to the paramagnetic phenyldiazenido-complex [ReBr2(NNPh)2(PPh3)2] 2 and its acetone solvate 2·Me2CO (formed in the presence of HSC6H2Pri3-2,4,6 or CNMe), and converted spontaneously (via a conceivable nucleophilic displacement at phenyldiazenide) into [ReBr3(NNPh)(PPh3)2] 3 from which 2 can also be derived. The molecular structure of 2 has been determined by X-ray diffraction analysis which indicates that one of the diazenide ligands is doubly bent and the other singly bent, each being trans to a bromide ligand and exerting a significant trans influence. Complexes 1–3 react with isocyanides to give the reduced mixed diazenido–isocyanide complexes [ReBr2(NNPh)(CNR)(PPh3)2] (R = Me 4 or C6H4Cl-4 5), [ReBr2(NNPh)(CNMe)2(PPh3)] 6 or [ReBr(NNPh)(CNMe)2(PPh3)2] 7.
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