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The reactions of several boron halides, methoxides, alkyls and hydrides with tris(tri-methylsilyl)silyllithium, which was isolated as the solvate [(CH 3 ) 3 Si] 3 SiLi ·  3 C 4 H 8 O, 1(TMSSLi) have been studied. (CH 3 ) 2 B−Si[Si(CH 3 ) 3 ] 3  and 9−[(CH 3 ) 3 Si] 3 Si-9-BBN, were isolated, while [(CH 3 ) 3 Si] 3 Si-B( t C 4 H 9 ) 2  could only be detected by  11 B NMR. In addition TMSS-B[N(CH 3 ) 2 ] 2 , (TMSS) 2 BNMe 2  and (TMSS) 2 BOCH 3  were prepared. The methoxy-boranes (CH 3 ) 3-n B(OCH 3 ) n  add to 1 forming silylborates; however, no OCH 3 /Si[Si(CH 3 ) 3 ] 3  substitution occurs. The hydrogen bridge in 9-BBN is cleaved symmetrically. The results can be explained by the basicity and the steric requirements of the TMSS group. The TMSS group exhibits a deshielding effect at the boron nucleus relative to the (CH 3 ) 3 Si group for silylboranes as well as for silylborates.

zeitschrift für naturforschung b

Beiträge zur Chemie des Bors, 124 [1] Tris(trimethylsilyl)silyl-borane und Tris(trimethylsilyl)silyl-borate / Contributions to the Chemistry of Boron, 124 [1] Tris(trimethylsilyl)silyl Boranes and Tris(trimethylsilyl)silyl Borates