Distinctly different reactivity of bis(silylenyl)-<i>versus</i> phosphanyl-silylenyl-substituted <i>o</i>-dicarborane towards O<sub>2</sub>, N<sub>2</sub>O and CO<sub>2</sub>
Yun Xiong, Shenglai Yao, Aleš Růžička, Matthias Drieß
Abstract
In stark contrast to the reactivity of the bis-silylenyl dicarborane CB-Si2 (1) [CB = ortho-C,C'-C2B10H10, Si = PhC(tBuN)2Si] towards O2, N2O, and CO2, yielding the same dioxygenation product CB-Si2O2 (2) with a four-membered 1,3,2,4-disiladioxetane ring, the activation of the latter small molecules with the phosphanyl-silylenyl-functionalised CB-SiP (3) {P[double bond, length as m-dash]P[N(tBu)CH2]2} affords with O2 the CB-Si([double bond, length as m-dash]O)P([double bond, length as m-dash]O) silanone-phosphine oxide (4), with N2O the CB-Si([double bond, length as m-dash]O)P silanone-phosphine (5), and with CO2 the CB-Si(O2C[double bond, length as m-dash]O)P silicon carbonate-phosphine (6) and CB-C([double bond, length as m-dash]O)OSiOP ester (7), respectively.