N-Heterocyclic carbene and cyclic (alkyl)(amino)carbene complexes of vanadium(III) and vanadium(V)
Günther Horrer1, Ivo Krummenacher1,2, Sophie Mann1
1Institute for Inorganic Chemistry, Julius-Maximilians-Universität Würzburg, Am Hubland, 97074 Würzburg, Germany. u.radius@uni-wuerzburg.de.
Abstract:
[VCl3(THF)3] offers a convenient entrance point into the chemistry of carbene stabilized V(III) complexes. Herein we report the paramagnetic mono- and biscarbene complexes [VCl3(cAACMe)] 1, [VCl3(cAACMe)(THF)] 1(thf), [VCl3(IMes)] 2, [{VCl2(IiPrMe)(μ-Cl)}2] 3, [VCl3(IDipp)] 4, [VCl3(SIDipp)] 5, [VCl3(SIDipp)(THF)] 5(thf), [VCl3(ItBu)] 6, [VCl3(cAACMe)2] 7 and [VCl3(IiPrMe)2] 8. Reaction of 1 with MesMgCl, MesLi and LiNPh2 afforded the complexes [VCl2(Mes)(cAACMe)] 9, [cAACMeH]+[VCl2Mes2]-10 and [VCl2(NPh2)(cAACMe)] 11. The V(V) complexes [V(O)Cl3(IDipp)] 12 and [V(O)Cl3(SIDipp)] 13 were selectively prepared from oxygen oxidation of 4 and 5. [V(O)Cl3(IDipp)] 12 and [V(O)Cl3(IMes)] react with isocyanates to yield the NHC-ligated imido complexes [V(N-p-CH3C6H4)Cl3(IDipp)] 14, [V(N-p-FC6H4)Cl3(IDipp)] 15, [V(N-p-CH3C6H4)Cl3(SIDipp)] 16, [V(N-p-FC6H4)Cl3(SIDipp)] 17, [V(N-p-CH3C6H4)Cl3(IMes)] 18 and [V(N-p-FC6H4)Cl3(IMes)] 19.
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