Preparation and properties of molybdenum and tungsten dinitrogen complexes: XLII. Preparation and characterization of W(V) diazoalkane complexesmer,trans-[WX3(NNCMeR)(PMe2Ph)2] (X Br, I; R Me, Ph) and hydrazido(2-) complex [WI3(NNH2)(PMe2Ph)2]. X-ray structure of mer,trans-[WBr3(NNCMePh)(PMe2Ph)2]

Abstract Reactions of W(IV) diazoalkane complexes cis,mer -[WX 2 (NNCMeR)(PMe 2 Ph) 3 ] (X  Br, I; R  Me, Ph) and hydrazido(2-) complex cis,mer -[WI 2 (NNH 2 )(PMe 2 Ph) 3 ] with five equivalents of CH 2 X 2 in toluene at 80°C gave paramagnetic W(V) complexes, mer,trans -[WX 3 (NNCMeR)(PMe 2 Ph) 2 ] and [WI 3 (NNH 2 )(PMe 2 Ph) 2 ] respectively. The latter complex was also obtained upon hydrolysis of a W(V) disilylhydrazido(2-) complex mer,trans -[WI 3 (N NSiMe 2 CH 2 CH 2 S iMe 2 )(PMe 2 Ph) 2 ] and was converted into mer,trans -[WI 3 (NNCMeR)(PMe 2 Ph) 2 ] by the subsequent condensation with RMeCO. The structure of mer,trans -[WBr 3 (NNCMePh)(PMe 2 Ph) 2 ] ( 6d ) was determined by X-ray analysis. Crystal data for 6d are as follows: monoclinic, space group P 2 1 / n with a = 9.900(3) A, b = 21.029(4) A, c = 13.950(2) A, β = 96.80(2)°, V = 2883.9(11) A 3 , Z = 4 and R = 0.060 for 4567 reflections.