Preparation and properties of molybdenum and tungsten dinitrogen complexes XLI. Silylation and germylation of a coordinated dinitrogen in cis- (M = Mo, W) using R3ECl/NaI and R3ECl/Na mixtures (E = Si, Ge). X-ray structure of trans-*C6H6

Article abstract of DOI:10.1016/0022-328X(93)80428-E

Treatment of cis- (1) with R3SiCl and excess NaI in benzene afforded a series of silyldiazenido complexes trans- (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-C6H4SiMe2NN)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- (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 P<*>1 with a = 13.533(3), b = 19.629(7), c = 11.941(6) Angstroem, α = 103.59(3), β = 116.11(3), γ = 81.12(2) deg, V = 2763.7(16) Angstroem³, 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, 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).