Addition of amines and hydroborane to the disilyne RSi[triple bond]SiR (R = Si(i)Pr[CH(SiMe3)2]2) giving amino- and boryl-substituted disilenes.
The reaction of 1,1,4,4-tetrakis[bis(trimethylsilyl)methyl]-1,4-diisopropyltetrasila-2-yne 1 with diethylamine or diphenylamine produced the corresponding amino-substituted disilenes R(R'(2)N)Si=SiHR 2a, b (R = Si(i)Pr[CH(SiMe(3))(2)](2), R' = Et (2a), Ph (2b)). The reaction of 1 with 9-borabicyclo[3.3.1]nonane afforded the boryl-substituted disilene R(R''(2)B)Si=SiHR 3 (R''(2)B = 9-borabicyclo[3.3.1]nonan-9-yl). Spectroscopic and X-ray crystallographic analyses of 2a, b, and 3 showed that 2a and 3 have a coplanar arrangement of the Si=Si double bond and amino or boryl groups, giving pi-conjugation between the Si=Si double bond and the lone pair on the nitrogen atom or vacant 2p orbital on the boron atom, whereas 2b exhibits no such conjugation.
Takeuchi
Katsuhiko
K
Department of Chemistry, Graduate School of Pure and Applied Sciences, University of Tsukuba, Tsukuba, Ibaraki 305-8571, Japan.
Ikoshi
Masao
M
Ichinohe
Masaaki
M
Sekiguchi
Akira
A