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.
Highlights
For many decades, the activation of ubiquitous small molecules such as H2, N2, O2, CO, CO2, N2O, etc. has been considered to be a domain of transition-metal chemistry and metalloenzymes, including their low molecular-weight functional models
Recent advances in low-valent non- and semi-metal chemistry have provided a plethora of impressive evidence with transition-metal-like reactivity of main-group elements in small molecule activation.[1,2,3,4,5,6]
This is in part due to the availability of reactive lone pair electrons and relatively low-lying empty acceptor orbitals of main-group elements in unusual low oxidation states, which can mimic the electronic situation of transition-metal centres and even mediate chemical bond cleavage of unactivated small molecules
Summary
The activation of ubiquitous small molecules such as H2, N2, O2, CO, CO2, N2O, etc. has been considered to be a domain of transition-metal chemistry and metalloenzymes, including their low molecular-weight functional models.
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