American Chemical Society
om6b00870_si_002.cif (1.6 MB)

Catalytic Acceptorless Dehydrogenation of Amines with Ru(PR2NR′2) and Ru(dppp) Complexes

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posted on 2017-04-20, 19:34 authored by James M. Stubbs, Richard J. Hazlehurst, Paul D. Boyle, Johanna M. Blacquiere
[Ru­(Cp)­(PPh2NBn2)­(MeCN)]­PF6 (1; PPh2NBn2 = 1,5-benzyl-3,7-phenyl-1,5-diaza-3,7-diphosphacyclooctane) and [Ru­(Cp)­(dppp)­(MeCN)]­PF6 (2; dppp = 1,3-bis­(diphenylphosphino)­propane) are both active toward the acceptorless dehydrogenation of benzylamine (BnNH2) and N-heterocycles. The two catalysts have similar activities but different selectivities for dehydrogenation products. Independent synthesis of a [Ru­(Cp)­(PPh2NBn2)­(NH2Bn)]­PF6 adduct (3) reveals the presence of a hydrogen bond between the bound amine and the pendent base of the PPh2NBn2 ligand. Preliminary mechanistic studies reveal that the benzylamine adduct is not an on-cycle catalyst intermediate.