Szych Lilian S, Bresien Jonas, Fischer Lukas, Ernst Moritz J, Goicoechea Jose M
Department of Chemistry, University of Oxford, Chemistry Research Laboratory 12 Mansfield Road Oxford OX1 3TA UK.
Institut für Chemie und Biochemie, Freie Universität Berlin Fabeckstraße 34/36 Berlin 14195 Germany.
Chem Sci. 2025 Mar 17;16(17):7397-7410. doi: 10.1039/d5sc00295h. eCollection 2025 Apr 30.
The synthesis of an arsanyl-phosphagallene [HCN(Dipp)]AsP[double bond, length as m-dash]Ga(NacNac) (NacNac = HC[C(Me)N(Dipp)]; Dipp = diisopropylphenyl) and its reactivity towards heterocumulenes and ketones is described. Reactions with azides, carbodiimides, isocyanates and ketones give rise to heterocycles cyclization reactions involving the Ga[double bond, length as m-dash]P π-bond (with the Ga-P σ-bond remaining unperturbed in the final products). By contrast, reactions with CO, CS and COS are more intriguing, revealing a reactivity profile in which the phosphorus atom can abstract carbon monoxide from the oxygen-containing heterocumulenes. These reactions result in the formation of gallium phosphaethynolate compounds. Such reactivity is enabled by the presence of a weakly Lewis basic arsanyl moiety which, in contrast to other related compounds featuring phosphanyl groups, is insufficiently nucleophilic to play a role in frustrated Lewis-pair like reactivity.
本文描述了一种芳基胂基-磷杂环丙烯[HCN(Dipp)]AsP═Ga(NacNac)（NacNac = HC[C(Me)N(Dipp)]；Dipp = 二异丙基苯基）的合成及其与杂累积二烯和酮的反应活性。与叠氮化物、碳二亚胺、异氰酸酯和酮的反应会产生杂环——涉及Ga═P π键的环化反应（在最终产物中Ga-P σ键保持不变）。相比之下，与CO、CS和COS的反应更有趣，揭示了一种反应活性模式，其中磷原子可以从含氧化杂累积二烯中夺取一氧化碳。这些反应导致形成镓磷乙炔醇盐化合物。这种反应活性是由一个弱路易斯碱性的芳基胂基部分的存在所促成的，与其他具有膦基的相关化合物相比，该部分亲核性不足，无法在类似受挫路易斯对的反应中发挥作用。
