Wilson Daniel W N, Myers William K, Goicoechea Jose M
Department of Chemistry, University of Oxford, Chemistry Research Laboratory, 12 Mansfield Road, Oxford, OX1 3TA, UK.
Department of Chemistry, University of Oxford, Centre for Advanced ESR, Inorganic Chemistry Laboratory, South Parks Road, Oxford, OX1 3QR, UK.
Dalton Trans. 2020 Nov 10;49(43):15249-15255. doi: 10.1039/d0dt03174g.
A series of gallium phosphaketenyl complexes supported by a 1,2-bis(aryl-imino)acenaphthene ligand (Dipp-Bian) are reported. Photolysis of one such species induced decarbonylation to afford a gallium substituted diphosphene. Addition of Lewis bases, specifically trimethylphosphine and the gallium carbenoid Ga(Nacnac) (Nacnac = HC[C(Me)N-(C6H3)-2,6-iPr2]2), resulted in displacement of the phosphaketene carbonyl to yield base-stabilised phosphinidenes. In several of these transformations, the redox non-innocence of the Dipp-Bian ligand was found to give rise to radical intermediates and/or side-products.
报道了一系列由1,2-双（芳基亚氨基）苊配体（Dipp-Bian）支撑的镓磷杂环丁二烯配合物。对其中一种此类物质进行光解会引发脱羰反应，从而得到一种镓取代的二膦烯。加入路易斯碱，特别是三甲基膦和镓卡宾Ga(Nacnac)（Nacnac = HC[C(Me)N-(C6H3)-2,6-iPr2]2），会导致磷杂环丁二烯羰基被取代，生成碱稳定的磷烯。在其中一些转化过程中，发现Dipp-Bian配体的氧化还原非无辜性会产生自由基中间体和/或副产物。
