Preparation and properties of molybdenum and tungsten dinitrogen complexes: XLI. Silylation and germylation of a coordinated dinitrogen in cis-[M(N 2) 2(PMe 2Ph) 4](M Mo, W) using R 3ECl/NaI and R 3ECl/Na mixtures (E  Si, Ge). X-ray structure of trans-[WI(NNGePh 3)(PMe 2Ph) 4]· C 6H 6

Abstract

Treatment of cis-[W(N 2) 2(PMe 2Ph) 4] ( 1) with R 3SiCl and excess NaI in benzene afforded a series of silyldiazenido complexes trans-[WI(NNSiR 3)(PMe 2Ph) 4](R 3  Me 3, EtMe 2,Et 3, Me 3- nPh n( n  1–3), (MeO)Me 2,(MeO) 2Me), while a dinuclear complex with bridging silyldiazenido ligand [(PhMe 2P) 4IW(NNSiMe 2- p-C 6H 4 SiMe 2NN)WI(PMe 2Ph) 4] was obtained from the reaction of 1 with p-ClMe 2SiC 6H 4SiMe 2Cl and NaI. Analogous treatment of 1 with a mixture of R 3GeCl and excess NaI gave novel germylated dinitrogen complexes trans-[WI(NNGeR 3)(PMe 2Ph) 4](R  Me, Ph ( 13)). The molecular structure of 13 · C 6H 6 was determined by an X-ray analysis. Crystal data for 13 · C 6H 6: triclinic, space group P 1 with a = 13.533(3), b = 19.629(7), c = 11.941(6) Å, α = 103.59(3), β = 116.11(3), γ = 81.12(2)°, V = 2763.7(16)Å 3 , Z = 2 and R = 0.042 for 7476 reflections. On the other hand, when a variety of chlorosilanes or Me 3GeCl was reacted with one equiv of Na in THF under nitrogen in the presence of a catalytic amount of cis-[Mo(N 2) 2(PMe 2Ph) 4], molecular nitrogen was converted into the N 1 products, whose yields, detected as NH 3 after hydrolysis, varied from 0.2 to 7.5 mol/Mo atom depending on the substituent in R 3ECl (ESi, Ge).