Abstract
Abstract Reaction of WCl6 with four equivalents of Me3SiNHCMe3 in benzene gives a low yield of [W(NCMe3)Cl3(NH2CMe3)2] for which the IR spectrum indicates a mer arrangement of metal trichlorides. Further dehydrohalogenation to give an amido ligand does not take place. The structure of the complex was determined by single-crystal X-ray diffraction methods. The crystals are monoclinic, space group C2/c with four molecules in a unit cell of dimensions a = 19.701(3), b = 9.674(2), c = 11.430(2) A and β = 116.40(1)°. The structure was solved by Patterson and Fourier methods and refined to an R value of 0.030. The tungsten atom is in a distorted octahedral environment comprising three mer chloro ligands, two trans t-butylamine ligands and a t-butylimido ligand. A crystallographic two-fold axis passes through Cl(1), W and Nt-butylimido. Observed distances are WNt-butylimido = 1.728(5), WNt-butylamine = 2.230(4), WCl(2)=2.407(1) and WCl(1) = 2.473(2)A. The Cl(2)WNt-butylamine bond angle is 99.0(1)°. The t-butylamine quaternary carbon, C(21), lies close to the equatorial plane thereby reducing methyl group contact with the t-butylimido methyls. Rotation about the N(2)C(21) bond positions the methyl groups C(22) and C(24) above and below the equatorial plane. The hydrogens on N(2) also lie above and below the plane. As a consequence of this arrangement the NH and Cl atoms are unfavourably placed for further dehydrohalogenation to occur.
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