Tripodal amido-titanium and -zirconium complexes containing a trisilylsilane-derived ligand framework
摘要:
A series of amido-titanium and -zirconium complexes containing a tripodal amide with a trisilylsilane ligand framework has been prepared. The primary isolable products in the reaction of SiMe (SiMe(2)NHR)(3) (R = 4-MeC(6)H(4), 2-FC6H4 or 4-MeOC(6)H(4)) with LiBu(n) and ZrCl4 in diethyl ether are the [Li(OEt(2))(2)Cl] adducts of which the five-co-ordinate complex [{(4-MeOC(6)H(4)NSiMe(2))(3)MeSi}Zr(mu Cl)(2)Li(OEt(2))(2)] and the six-co-ordinate [{(2-FC(6)H(4)NSiMe(2))(3)MeSi}Zr(mu-Cl)(2)Li(OEt(2))(2)] have been characterised by X-ray crystallography. In the latter one of the fluorine atoms of the peripheral 2-FC6H4 groups is weakly coordinated to the metal. Stirring of the (Et(2)O)(2)LiCl adducts in toluene generates the four-co-ordinate complexes [Zr{SiMe(SiMe(2)NR)(3)}Cl]. Upon reaction of [M{SiMe[SiMe(2)N(C6H4F-2)](3)}Cl] (M = Ti or Zr) with AgO3SCF3 the corresponding triflates were obtained which are sufficiently stable to be isolated, The halide ligand may be readily substituted to give the corresponding methyl, ethynyl and cyclopentadienyl complexes.
Tripodal amido-titanium and -zirconium complexes containing a trisilylsilane-derived ligand framework
摘要:
A series of amido-titanium and -zirconium complexes containing a tripodal amide with a trisilylsilane ligand framework has been prepared. The primary isolable products in the reaction of SiMe (SiMe(2)NHR)(3) (R = 4-MeC(6)H(4), 2-FC6H4 or 4-MeOC(6)H(4)) with LiBu(n) and ZrCl4 in diethyl ether are the [Li(OEt(2))(2)Cl] adducts of which the five-co-ordinate complex [{(4-MeOC(6)H(4)NSiMe(2))(3)MeSi}Zr(mu Cl)(2)Li(OEt(2))(2)] and the six-co-ordinate [{(2-FC(6)H(4)NSiMe(2))(3)MeSi}Zr(mu-Cl)(2)Li(OEt(2))(2)] have been characterised by X-ray crystallography. In the latter one of the fluorine atoms of the peripheral 2-FC6H4 groups is weakly coordinated to the metal. Stirring of the (Et(2)O)(2)LiCl adducts in toluene generates the four-co-ordinate complexes [Zr{SiMe(SiMe(2)NR)(3)}Cl]. Upon reaction of [M{SiMe[SiMe(2)N(C6H4F-2)](3)}Cl] (M = Ti or Zr) with AgO3SCF3 the corresponding triflates were obtained which are sufficiently stable to be isolated, The halide ligand may be readily substituted to give the corresponding methyl, ethynyl and cyclopentadienyl complexes.