155019-61-7Relevant articles and documents
Synthesis of molybdenum and tungsten complexes that contain triamidoamine ligands of the type (C6F5NCH2CH2)3N and activation of dinitrogen by molybdenum
Kol, Moshe,Schrock, Richard R.,Kempe, Rhett,Davis, William M.
, p. 4382 - 4390 (1994)
Three new ligands of the type (ArNHCH2CH2)3N(Ar = 3,5-bis(trifluoromethyl)phenl,2-(trifluomethyl)-phenyl, and pentafluorophenyl) have been prepared. Only Mo and W complexes containing the [(C6F5NCH2CH2)3N] 3- ([N3N]3-) ligand were found to be stable. Stable complexes that have been prepared include Mo[N3N](NMe2), M[N3N]Cl (M = Mo or W), Mo[N3N](OTf) (M = Mo or W), [N3N]M≡N (M = Mo or W), and {[N3N]Mo=NMe}-(Otf). An X-ray study of Mo[N3N]Cl showed it to be a monomeric distorted trigonal bipyramidal species having a pseudo-C3 symmetry (space group P1, a = 11.265(2) ?, b = 11.371(2) ?, c = 21.805(4) ?, α = 82.40(1)°, β = 79.07(1)°, γ = 74.89(1)°, V = 2637.4 ?3, Z = 4, fw = 772.75, ρ(calcd) = 1.946 g/cm3, R = 0.032, Rw = 0.034). Reduction of Mo[N3N](OTf) with 1 equiv of sodium amalgam yields a dinuclear bridging dinitrogen species, [N3N]-Mo(μ-N2)Mo[N3N]. In the presence of 2 equiv of sodium amalgam in ether Mo[N3N](Otf) is reduced to [N3N]-Mo(N2) [Na(ether)x] (1 3N]Mo(μ-N2)Mo[N3N] can be reduced to [N3N]Mo(N2)[NaLx] by sodium amalgam under dinitrogen and the latter can be oxidized to the former by ferrocenium triflate or air. [N3N]Mo(N2)[NaLx] reacts with Mo[N3N](OTf) to give [N3N]Mo(μ-N2)Mo[N3N], with triisopropylsilyl chloride to give [N3N]MoN=NSi(i-Pr)3, and with tributyltin chloride to give [N3N]MoN=NSn(Bu)3. An X-ray study of [N3N]MoN=NSi(i-Pr)3(space group P21/n, a= 13.524-(3) ?, b = 18.016(4) ?, c = 16.248(3) ?, β = 98.74(2)°, V = 3913(1) ?3 = 4, fw = 922.67, ρ(calcd) = 1.566 g/cm3, R = 0.069 Rw = 0.072) showed it to be a trigonal bipyramidal complex containing a slightly bent diazenido ligand (Mo-Nα = 1.788(9) ?, Mo-Nα-Nβ = 171.1(8)°, Nα-Nβ-Si = 154(1)°).
