Unexpected White Phosphorus (P4) Activation Modes with Silylene‐Substitutedo‐Carboranes and Access to an Isolable 1,3‐Diphospha‐2,4‐disilabutadiene
Angewandte Chemie (International ed in English)(2022)
摘要
AbstractNew types of metal‐free white phosphorus (P4) activation are reported. While the phosphine‐silylene‐substituted dicarborane1, CB‐SiP(CB=ortho‐C,C′‐C2B10H10,Si=PhC(tBuN)2Si,P=P[N(tBu)CH2]2), activates white phosphorus in a 2 : 1 molar ratio to yield the P5‐chain containing species2, the analogous bis(silylene)‐substituted compound3, CB‐Si2,reacts with P4in the molar ratio of 2 : 1 to furnish the first isolable 1,3‐diphospha‐2,4‐disilabutadiene (Si=P−Si=P‐containing) compound4. For the latter reaction, two intermediates having a CB‐Si2P4and CB‐Si2P2core could be observed by multinuclear NMR spectroscopy. The compounds2and4were characterized including single‐crystal X‐ray diffraction analyses. Their electronic structures and mechanisms were investigated by density functional theory calculations.
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关键词
Metal-Free Hydrogen Activation
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