Wiley InterScience Backfile Collection 1832-2000
Chemistry and Pharmacology
Di-tert-butylmethylsilylamide reacts with n-BuLi to give the tetrameric lithium di-tert-butylmethylsilylamide 1. Reactions of lithium (di-tert-butylmethylsilyl)amide 1 with SiF4 give the mono- (2), bis- (3), tris- (4), and tetrakis- (5) -[(di-tert-butylmethylsilyl)amino]silanes. Lithiated 3 reacts with Me3SiCl to form (di-tert-butylmethylsilyl-trimethylsilyl)amino-(di-tert-butylmethylsilyl)amino-difluorosilane (6); the 1,3-diaza-2,4-disilacyclobutane 7 is obtained by LiF elimination. The lithium derivative of 6 (compound 8) crystallizes with formation of a (SiFNLi) four-membered ring system. The 19F-NMR spectrum proves that the Li-F bond fluctuates in solution. Reactions of 1 with (Me3Si)2C(SiF3)2 afford different products (9, 10) by controlling the reaction sequence. An excess of 1 reacts to give a four-membered CSi2N ring system, the 1-(di-tert-butylmethylsilyl)-2,4-bis-[(di-tert-butylmethylsilyl)-amino]-2,4-difluoro-3-bis(trimethylsilyl)-1-aza-2,4-disila-cyclobutane (9), disubstitution with formation of bis[(di-tert-butylmethylsilyl)aminodifluorosilyl]bis(trimethylsilyl)methane (10) occurs in a molar ratio of 2:1. The cyclodisilazane 11 is obtained from dilithiated 10 in an intramolecular interconversion reaction. The crystal structures of 1, 8, 9, and 11 are reported.
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