Reactivity of [Ce(NR<sub>2</sub>)<sub>3</sub>] (R = SiMe<sub>3</sub>) with Prospective Carbon Atom Transfer Reagents
Greggory T. Kent, Selena L. Staun, Guang Wu, Trevor W. Hayton
Abstract
Herein, we report the synthesis, characterization, and reactivity of the N-(isocyanoimine)triphenylphosphine (CNNPPh3) and bis(diisopropylamino)cyclopropenylidene (BAC) adducts of [Ce(NR2)3] (R = SiMe3): namely, [(NR2)3Ce(CNNPPh3)] (1) and [(NR2)3Ce(BAC)] (2), respectively. Photolysis of 1 with a 380 nm LED source for 1 month results in clean formation of [(NR2)3Ce(NCNPPh3)] (3), via reorganization of the nitrilimine ligand to its carbodiimide isomer. Photolysis of 2 with a 365 nm LED source results in formation of the methylenecyclopropene species [(iPr2N)2C3C(NiPr2)(CCNiPr2)] (5) via the formal dimerization and rearrangement of two BAC fragments. Compound 5 can also be generated under catalytic conditions by performing the photolysis of BAC in the presence of 10 mol % of [Ce(NR2)3].