FULLY CHLORINATED N-SILYL AMIDES OF TITANIUM AND TUNGSTEN - CRYSTAL-STRUCTURE OF CL3SINW(CL-3)N(SICL3)(2)

The reaction of hexachlorodisilazanyllithium (Cl-3,Si)(2)NLi (1), with TiCl4 leads selectively to the novel fully chlorinated amides (Cl3Si) (2)NTiCl3 (2) or [(Cl3Si)(2)N](2)TiCl2 (3), respectively, depending on the molar ratio of the starting materials. The analogous reaction of 1 with WCl6 yielded the amide imide Cl3SiN=W(Cl-3)N(SiCl3)(2) (5) by e limination of SiCl4. The relative amounts of the starting materials ha d no effect on the formation of 5. N-14/15-and Si-29-NMR data on the s tarting materials and products show significantly different effects, w hen compared with those of analogous N-trimethylsilyl derivatives, due to the lower energy of the electrons in the N-Si and N-M sigma bonds. The crystal structure of 5 (triclinic, space group <P(1)over bar>) wa s determined by X-ray structure analysis.