Preparation and properties of molybdenum and tungsten dinitrogen complexes: XLII. Preparation and characterization of W(V) diazoalkane complexes mer,trans-[WX 3(NNCMeR)(PMe 2Ph) 2] (X  Br, I; R  Me, Ph) and hydrazido(2-) complex [WI 3(NNH 2)(PMe 2Ph) 2]. X-ray structure of mer,trans-[WBr 3(NNCMePh)(PMe 2Ph) 2

Abstract

Reactions of W(IV) diazoalkane complexes cis,mer-[WX 2(NNCMeR)(PMe 2Ph) 3] (X  Br, I; R  Me, Ph) and hydrazido(2-) complex cis,mer-[WI 2(NNH 2)(PMe 2Ph) 3] with five equivalents of CH 2X 2 in toluene at 80°C gave paramagnetic W(V) complexes, mer,trans-[WX 3(NNCMeR)(PMe 2Ph) 2] and [WI 3(NNH 2)(PMe 2Ph) 2] respectively. The latter complex was also obtained upon hydrolysis of a W(V) disilylhydrazido(2-) complex mer,trans-[WI 3(N NSiMe 2CH 2CH 2S iMe 2)(PMe 2Ph) 2] and was converted into mer,trans-[WI 3(NNCMeR)(PMe 2Ph) 2] by the subsequent condensation with RMeCO. The structure of mer,trans-[WBr 3(NNCMePh)(PMe 2Ph) 2] ( 6d) was determined by X-ray analysis. Crystal data for 6d are as follows: monoclinic, space group P2 1/ n with a = 9.900(3) Å, b = 21.029(4) Å, c = 13.950(2) Å, β = 96.80(2)°, V = 2883.9(11) Å 3, Z = 4 and R = 0.060 for 4567 reflections.