Characterization of the "Absent" Vanadium Oxo V(═O){N(SiMe3)2}3, Imido V(═NSiMe3){N(SiMe3)2}3, and Imido-Siloxy V(═NSiMe3)(OSiMe3){N(SiMe3)2}2 Complexes Derived from V{N(SiMe3)2}3 and Kinetic Study of the Spontaneous Conversion of the Oxo Complex into Its Imido-Siloxy Isomer.The synthesis and characterization of V(═O){N(SiMe3)2}3 (1), V(═NSiMe3){N(SiMe3)2}3 (2), and V(═NSiMe3)(OSiMe3){N(SiMe3)2}2 (3) are described.  Prior attempts to synthesize the vanadium(V) oxo complex 1 via salt metathesis of VOCl3 with the lithium or sodium silylamide salt had yielded either the putative rearranged species V(═NSiMe3)(OSiMe3){N(SiMe3)2}2 (3) or the oxo-bridged, dimetallic {(μ-O)2V2[N(SiMe3)2]4}.  We now show that complex 1 is available by treatment of the vanadium(III) tris(silylamide) V{N(SiMe3)2}3 with iodosylbenzene.  The imido complex 2 was obtained by treatment of V{N(SiMe3)2}3 with trimethylsilyl azide.  Sublimation of 1 formed complex 3, which was determined to be V(═NSiMe3)(OSiMe3){N(SiMe3)2}2, on the basis of infrared, electronic, and 1H and 51V NMR spectroscopies.  Crystallographic disorder precluded a complete structural characterization of 3, although a four-coordinate V atom, as well as severely disordered ligands, were apparent.  Comparison of the vibrational spectra of 1 and 2 allowed an unambiguous assignment of the V-O (995 cm-1) and V-Nimide (1060 cm-1) stretching bands.  The vibrational spectrum of complex 3 displayed strong absorbances at 1090 and 945 cm-1, indicative of its metal imide and metal siloxide moieties.  The 1H NMR spectrum of 1 in deuterated benzene showed overlapping signals for the ligand protons proximal and distal to the oxo moiety at 0.52 and 0.38 ppm.  The 1H NMR spectrum of 2 in deuterated methylene chloride displayed distinct signals for the imido (0.41 ppm) and amido (0.35 ppm) protons, whereas 1H NMR spectroscopy of 3 showed three signals in an intensity ratio consistent with the formula V(═NSiMe3)(OSiMe3){N(SiMe3)2}2.  51V NMR spectra of 1-3 revealed singlet resonances at -119 ppm (1), -24 ppm (2), and -279 ppm (3).  The electronic spectra of 1-3 displayed single absorbances in the charge transfer region, consistent with their d0 electron configurations.  Kinetic studies of the spontaneous conversion of complex 1 to 3 were used to determine the rate constants (ca.  0.0002 s-1 (63 °C), 0.0006 s-1 (73 °C), 0.002 s-1 (83 °C)) and activation energy (ca. 20 kcal/mol) of this first-order process.
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