Ward Benjamin D, Dubberley Stuart R, Gade Lutz H, Mountford Philip
Inorganic Chemistry Laboratory, University of Oxford, South Parks Road, Oxford OX1 3QR, U.K., and Laboratoire de Chimie Organométallique et de Catalyse UMR 7513, Institut Le Bel, Université Louis Pasteur, 4, rue Blaise Pascal, 67000 Strasbourg, France.
Inorg Chem. 2003 Aug 11;42(16):4961-9. doi: 10.1021/ic034377s.
Reactions of the lithiated diamido-pyridine or diamido-amine ligands Li(2)N(2)N(py) or Li(2)N(2)N(am) with [W(NAr)Cl(4)(THF)] (Ar = Ph or 2,6-C(6)H(3)Me(2); THF = tetrahydrofuran) afforded the corresponding imido-dichloride complexes [W(NAr)(N(2)N(py))Cl(2)] (R = Ph, 1, or 2,6-C(6)H(3)Me(2), 2) or [W(NAr)(N(2)N(am))Cl(2)] (R = Ph, 3, or 2,6-C(6)H(3)Me(2), 4), respectively, where N(2)N(py) = MeC(2-C(5)H(4)N)(CH(2)NSiMe(3))(2) and N(2)N(am) = Me(3)SiN(CH(2)CH(2)NSiMe(3))(2). Subsequent reactions of 1 with MeMgBr or PhMgCl afforded the dimethyl or diphenyl complexes [W(NPh)(N(2)N(py))R(2)] (R = Me, 5, or Ph, 6), respectively, which have both been characterized by single crystal X-ray diffraction. Reactions of Li(2)N(2)N(py) or Li(2)N(2)N(am) with [Mo(NR)(2)Cl(2)(DME)] (R = (t)Bu or Ph; DME = 1,2-dimethoxyethane) afforded the corresponding bis(imido) complexes [Mo(NR)(2)(N(2)N(py))] (R = (t)Bu, 7, or Ph, 8) and [Mo(N(t)Bu)(2)(N(2)N(am))] (9).
锂化的二氨基吡啶或二氨基胺配体Li₂N₂N(py)或Li₂N₂N(am)与[W(NAr)Cl₄(THF)]（Ar = Ph或2,6-C₆H₃Me₂；THF = 四氢呋喃）反应，分别得到相应的亚氨基二氯化物配合物[W(NAr)(N₂N(py))Cl₂]（R = Ph，1，或2,6-C₆H₃Me₂，2）或[W(NAr)(N₂N(am))Cl₂]（R = Ph，3，或2,6-C₆H₃Me₂，4），其中N₂N(py) = MeC(2-C₅H₄N)(CH₂NSiMe₃)₂且N₂N(am) = Me₃SiN(CH₂CH₂NSiMe₃)₂。随后1与MeMgBr或PhMgCl反应，分别得到二甲基或二苯基配合物[W(NPh)(N₂N(py))R₂]（R = Me，5，或Ph，6），二者均已通过单晶X射线衍射表征。Li₂N₂N(py)或Li₂N₂N(am)与[Mo(NR)₂Cl₂(DME)]（R = (t)Bu或Ph；DME = 1,2-二甲氧基乙烷）反应，得到相应的双（亚氨基）配合物[Mo(NR)₂(N₂N(py))]（R = (t)Bu，7，或Ph，8）和[Mo(N(t)Bu)₂(N₂N(am))]（9）。
