Multi‐Talented Gallaphosphene for Ga−P−Ga Heteroallyl Cation Generation, CO<sub>2</sub> Storage, and C(sp<sup>3</sup>)−H Bond Activation
Mahendra K. Sharma, Christoph Wölper, Gebhard Haberhauer, Stephan Schulz
Abstract
Abstract Gallaphosphene L(Cl)GaPGaL ( 2 ; L=HC[C(Me)N(2,6‐ i ‐Pr 2 C 6 H 3 )] 2 ), which is synthesized by reaction of LGa(Cl)PCO ( 1 ) with LGa, reacts with [Na(OCP)(dioxane) 2.5 ] to LGa(OCP)PGaL ( 3 ), whereas chloride abstraction with LiBAr F 4 yields [LGaPGaL][BAr F 4 ] ( 4 ; BAr F 4 =B(C 6 F 5 ) 4 ). 4 represents a heteronuclear analog of the allyl cation according to quantum chemical calculations. Remarkably, 2 reversibly reacts with CO 2 to yield L(Cl)Ga−P[μ‐C(O)O] 2 GaL ( 5 ), while reactions with acetophenone and acetone selectively give compounds 6 and 7 by C(sp 3 )−H bond activation.
Topics & Concepts
Heteronuclear moleculeAcetophenoneAcetoneChemistryMedicinal chemistryYield (engineering)Bar (unit)ChlorideBond lengthStereochemistryCrystallographyNuclear magnetic resonance spectroscopyCrystal structureOrganic chemistryCatalysisMaterials sciencePhysicsMeteorologyMetallurgyOrganoboron and organosilicon chemistrySynthesis and characterization of novel inorganic/organometallic compoundsInorganic Fluorides and Related Compounds