Organo-silicon compounds S 0060 Synthesis, Molecular and Crystal Structures, and Characteristic Features of Electronic Structures of Salicylamide-Based B, Si-Containing Chelates. -(KORLYUKOV*, A. A.; LYSSENKO, K. A.; ANTIPIN, M. Y.; SHIPOV, A. G.; ZAMYSHLYAEVA, O. A.; KRAMAROVA, E. P.; NEGREBETSKY, V. V.; POGOZHIKH, S. A.; OVCHINNIKOV, Y. E.; BAUKOV, Y. I.; Russ.
Most of the presently known N-silylmethyl derivatives of amides and related compounds containing at least one fairly electronegative substituent at the silicon atom are characterized by an O--Si chelate structure with an intramolecular O~Si coordination bond. 1,z Much less is known about intermolecular homoassociates with the participation of these compounds. 2Previously, 3 we have described N-(chlorodimethylsilylmethyl)acetamide (la), which is the first representative of monosubstituted amides of the general formula RC(O)NHCH2SiMe2X. Coordination interactions in these compounds can occur not only through the oxygen atom of the amide group but also through the hydrogen atom of the NH group and can, in principle, lead to ir~terrno[ecular hydrogen bonding_ that affects intramolecular coordination bonds. The data of JH and 29Si NMR and IR spectroscopy provided evidence for the existence of intramolecular O--,Si coordination bonds only in concentrated solutions of chloride la. The structure of the latter in the crystalline state has not been studied due to problems associated with the preparation of crystals suitable for X-ray diffraction study.In the present work, previously unknown monosubstituted N-(fluorodimethylsilylmethyl)amides 3a,b were synthesized from chlorides la,b (prepared from the cor- responding N-trimethylsilytamides by transsilylation)* through intermediate disiloxanes 2a,b (Scheme I). The reasonable data of elemental analysis were obtained for all isolated compounds except for ch}oride la. The crystal structures of fluorides 3a,b were established by X-ray diffraction analysis and confirmed by the data of *The multistage scheme of these transsilylation reactions was discussed in detail in the review, t
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