Feld Joey, Yang Eric S, Urwin Stephanie J, Goicoechea Jose M
Department of Chemistry, University of Oxford, Chemistry Research Laboratory, 12 Mansfield Road, Oxford, OX1 3TA, United Kingdom.
Department of Chemistry, Indiana University, 800 E. Kirkwood Ave., Bloomington, IN 47405, U.S.A.
Chemistry. 2024 Aug 19;30(46):e202401736. doi: 10.1002/chem.202401736. Epub 2024 Jul 26.
Reaction of a nucleophilic germylene Ge[CH(SiMe)] with the phosphanyl phosphaketene [{(HC)(NDipp)}P]PCO induces decarbonylation to form a phosphanyl phosphagermene [{(HC)(NDipp)}P]P=Ge[CH(SiMe)] (1; Dipp=2,6-diisopropyl-phenyl). Addition of CO or MeCN to 1 results in [3+2]-cycloaddition reactions to afford five-membered heterocycles. This mode of reactivity is reminiscent of that observed for frustrated Lewis pairs, with the pendant phosphanyl group acting as a base and the germanium center as a Lewis acid. Contrastingly, 1,2-addition across the P=Ge bond was observed when using ammonia, small primary amines (NH P), or metal complexes (e. g. Au(PPh)Cl and ZnEt). These latter reactions allow for the one-step synthesis of metal phosphide complexes.
亲核性亚锗烯Ge[CH(SiMe)]与膦基磷酮[{(HC)(NDipp)}P]PCO反应会引发脱羰反应，形成膦基磷锗烯[{(HC)(NDipp)}P]P=Ge[CH(SiMe)]（1；Dipp = 2,6 - 二异丙基苯基）。向1中加入CO或MeCN会引发[3 + 2]环加成反应，生成五元杂环。这种反应模式让人联想到受阻路易斯酸碱对所观察到的情况，其中悬垂的膦基作为碱，锗中心作为路易斯酸。相比之下，当使用氨、小的伯胺（NH P）或金属配合物（例如Au(PPh)Cl和ZnEt）时，会观察到P=Ge键上的1,2 - 加成反应。这些后续反应允许一步合成金属磷化物配合物。
