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The reaction of O-trimethylsilyl-1,1-dimethyl-2-trifluoroacetylhydrazine (1a) with chloromethyl(methyl)dichlorosilane affords an unexpected equilibrium mixture, 10a right arrow over left arrow 11a, between a neutral hexacoordinate silicon chelate with a covalent chloro ligand (10a) and an ionic pentacoordinate silicon complex (11a). The equilibrium reaction consists formally of a migration of the covalent chloro ligand from silicon to an adjacent ammonium nitrogen, as a chloride anion, and thus constitutes a novel type of tautomeric reaction. Crystallographic and NMR data provide evidence for the reaction. Temperature, solvent, substituent, and counterion effects on the tautomeric equilibrium are discussed: when the temperature of the mixture is raised, the equilibrium ratio 10a/11a increases. Formation of the mixture in toluene, a nonionizing solvent, shifts the equilibrium completely toward the neutral 10a. When the initial hydrazide has a phenyl (11c) or a hydrogen (11b) group as substituent, rather than CF3, the equilibrium is shifted to the ionic side. Replacement of the chloride counterion by triflate, using trimethylsilyl triflate, shifts the 10a/11a mixture to the ionic side. Low-temperature NMR monitoring of the stepwise formation of 10/11 was carried out and provided insight into the reaction mechanism. In an attempt to grow crystals of 11c, the pentacoordinate tautomer analogue, an unprecedented chloride-bridged disiloxane complex, with two pentacoordinate silicons sharing a common axial chloro ligand, crystallized and was characterized and described.

The reaction of (chloromethyl)trichlorosilane (7) with O-trimethylsilylated N,N-dimethylhydrazides yields initially under kinetic control, in nearly quantitative yields, a neutral hexacoordinate bis(NfSi) chelate, bis(N-(dimethylamino)acylimidato-N,O)chloro(chloromethyl)silicon(IV) (8a-c). Upon heating, the octahedral complexes 8 are quantitatively and irreversibly converted to the isomeric hexacoordinate chelates zwitterionic λ 6 -silicates 9a-c, (N-(dimethylamino). This molecular rearrangement is rather unusual, since it involves chelatering expansion from the common five-membered ring to a six-membered ring in the thermodynamically favored product 9. 8b and 9b were characterized by X-ray crystal analyses and in solution by their 1 H, 13 C, and 29 Si NMR spectra. The analogous compounds 8a,c and 9a,c were characterized by the respective analogy of their NMR spectra. Both 8b and 9b have slightly distorted octahedral geometries around the central silicon atom. Both series of chelates 8 and 9 undergo ligand-site exchange processes, observed by the coalescence of signals due to diastereotopic N-methyl and/or CH 2 groups. Each compound (of both series) undergoes two consecutive rate processes: in 8 this sequence of exchange processes is analogous to previously reported stereomutations through a bicapped-tetrahedral intermediate or transition state; in 9 the first (lower barrier) process is a nitrogen-silicon dissociationrecombination, and the high-barrier process is an inversion of configuration at the silicon center.We have recently utilized the reaction of O-(trimethylsilyl)-N,N-dimethylhydrazides (1) with polyhalosilanes as a convenient method for the synthesis of a variety of different penta-and hexacoordinate silicon complexes with NfSi coordination (eq 1). 1-9 1 functions as a precursor for five-membered NfSi chelate rings.On the other hand, when 1 was allowed to react with (chloromethyl)dimethylchlorosilane (4; eq 2), OfSi coordinated complexes with five-and six-membered chelate cycles (6 and 5, respectively) were obtained. 10-13 † Ben-Gurion University. Kalikhman, I.; Krivonos, S.; Stalke, D.; Kottke, T. J. Am. Chem. Soc. 1998, 120, 4209. (7) Mozzhukhin, A. O.; Antipin, M. Yu.; Struchkov, Yu. T.; Gostevskii, B. A.; Kalikhman, I. D.; Pestunovich, V. A.; Voronkov, M. G. Bannikova, O. B.; Petuchov, L. P.; Pestunovich, V. A.; Voronkov, M. G. Dokl. Akad. Nauk SSSR 1986, 287, 870. (11) Kalikhman, I. D.; Pestunovich, V. A.; Gostevskii, B. A.; Bannikova, O. B.; Voronkov, M. G. J. Organomet. Chem. 1988, 338, 169. (12) Macharashvili, A. A.; Shklover, V. E.; Struchkov, Yu. T.; Gostevskii, B. A.; Kalikhman, I. D.; Bannikova, O. B.; Voronkov, M. G.; Pestunovich, V. A.

Novel chelating agents derived from N-isopropylidene hydrazides, N-isopropylideneimino-O-(trimethylsilyl)acylimidates ( 1), have been utilized to prepare hexacoordinate dihalosilicon complexes (2) unique in their trans geometry and in their facile ionization to pentacoordinate siliconium halide salts (3).

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