用于生成Ga-P-Ga杂烯丙基阳离子、储存CO以及活化C(sp) -H键的多功能镓磷烯

Sharma Mahendra K, Wölper Christoph, Haberhauer Gebhard, Schulz Stephan

Institute of Inorganic Chemistry and Center for Nanointegration Duisburg-Essen (CENIDE), University of Duisburg-Essen, Universitätsstrasse 5-7, 45141, Essen, Germany.

Institute of Organic Chemistry, University of Duisburg-Essen, Universitätsstrasse 5-7, 45141, Essen, Germany.

Angew Chem Int Ed Engl. 2021 Mar 15;60(12):6784-6790. doi: 10.1002/anie.202014381. Epub 2021 Jan 28.

Gallaphosphene L(Cl)GaPGaL (2; L=HC[C(Me)N(2,6-i-Pr C H )] ), which is synthesized by reaction of LGa(Cl)PCO (1) with LGa, reacts with [Na(OCP)(dioxane) ] to LGa(OCP)PGaL (3), whereas chloride abstraction with LiBAr yields [LGaPGaL][BAr ] (4; BAr =B(C F ) ). 4 represents a heteronuclear analog of the allyl cation according to quantum chemical calculations. Remarkably, 2 reversibly reacts with CO to yield L(Cl)Ga-P[μ-C(O)O] GaL (5), while reactions with acetophenone and acetone selectively give compounds 6 and 7 by C(sp )-H bond activation.

镓膦烯L(Cl)GaPGaL (2; L=HC[C(Me)N(2,6-i-Pr₂C₆H₃)]₂) 由LGa(Cl)PCO (1) 与LGa反应合成，它与[Na(OCP)(二氧六环)₂]反应生成LGa(OCP)PGaL (3)，而用LiBArF₂进行氯原子抽取则得到[LGaPGaL][BArF₂] (4; BArF₂ =B(C₆F₅)₄)。根据量子化学计算，4代表烯丙基阳离子的异核类似物。值得注意的是，2与CO可逆反应生成L(Cl)Ga-P[μ-C(O)O]GaL (5)，而与苯乙酮和丙酮反应则通过C(sp³)-H键活化选择性地生成化合物6和7。