Hiroyuki Oshita

Preparation and properties of molybdenum and tungsten dinitrogen complexes: XLI. Silylation and germylation of a coordinated dinitrogen in cis-[M(N2)2(PMe2Ph)4](M Mo, W) using R3ECl/NaI and R3ECl/Na mixtures (E Si, Ge). X-ray structure of trans-[WI(NNGePh3)(PMe2Ph)4]· C6H6☆

Treatment of cis-[W(N2)2(PMe2Ph)4] (1) with R3SiCl and excess NaI in benzene afforded a series of silyldiazenido complexes trans-[WI(NNSiR3)(PMe2Ph)4](R3  Me3, EtMe2,Et3, Me3-nPhn(n  1–3), (MeO)Me2,(MeO)2Me), while a dinuclear complex with bridging silyldiazenido ligand [(PhMe2P)4IW(NNSiMe2-p-C6H4 SiMe2NN)WI(PMe2Ph)4] was obtained from the reaction of 1 with p-ClMe2SiC6H4SiMe2Cl and NaI. Analogous treatment of 1 with a mixture of R3GeCl and excess NaI gave novel germylated dinitrogen complexes trans-[WI(NNGeR3)(PMe2Ph)4](R  Me, Ph (13)). The molecular structure of 13 · C6H6 was determined by an X-ray analysis. Crystal data for 13 · C6H6: triclinic, space group P1 with a = 13.533(3), b = 19.629(7), c = 11.941(6) A, α = 103.59(3), β = 116.11(3), γ = 81.12(2)°, V = 2763.7(16)A3 , Z = 2 and R = 0.042 for 7476 reflections. On the other hand, when a variety of chlorosilanes or Me3GeCl was reacted with one equiv of Na in THF under nitrogen in the presence of a catalytic amount of cis-[Mo(N2) 2(PMe2Ph)4], molecular nitrogen was converted into the N1 products, whose yields, detected as NH3 after hydrolysis, varied from 0.2 to 7.5 mol/Mo atom depending on the substituent in R3ECl (ESi, Ge).

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-[WX2(NNCMeR)(PMe2Ph)3] (X  Br, I; R  Me, Ph) and hydrazido(2-) complex cis,mer-[WI2(NNH2)(PMe2Ph)3] with five equivalents of CH2X2 in toluene at 80°C gave paramagnetic W(V) complexes, mer,trans-[WX3(NNCMeR)(PMe2Ph)2] and [WI3(NNH2)(PMe2Ph)2] respectively. The latter complex was also obtained upon hydrolysis of a W(V) disilylhydrazido(2-) complex mer,trans-[WI3(N NSiMe 2 CH 2 CH 2 S iMe2)(PMe2Ph)2] and was converted into mer,trans-[WI3(NNCMeR)(PMe2Ph)2] by the subsequent condensation with RMeCO. The structure of mer,trans-[WBr3(NNCMePh)(PMe2Ph)2] (6d) was determined by X-ray analysis. Crystal data for 6d are as follows: monoclinic, space group P21/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) A3, Z = 4 and R = 0.060 for 4567 reflections.