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PNN' & P2NN' ligands via reductive amination with phosphine aldehydes: synthesis and base-metal coordination
Matthew V Gradiski1, Brian T H Tsui, Alan J Lough
1Department of Chemistry, University of Toronto, 80 Saint George Street, Toronto, Ontario M5S 3H6, Canada. rmorris@chem.utoronto.ca.
Abstract:
Novel PNN' & P2NN' ligands based on 2-aminopyridine (APyPNN-R) R = Ph (1a), Cy (1b), iBu (1c), 8-aminoquinoline (AQPNN-R) R = Ph (2a), Cy (2b), iBu (2c), iPr (2d), and 2-picolylamine (P2NN-R) R = Ph (3a), Cy (3b), iBu (3c), have been synthesized via a versatile, one-pot, single-step, reductive amination of tertiary phosphine acetaldehydes with the amine by reaction with STAB (where STAB is sodium(triacetoxy)borohydride). Ligands 1b and 1c bridge between paramagnetic Co(ii) and form dimeric complexes Co2Cl4(APyPNN-R)2 (4 and 5) when reacted with cobalt dichloride. Ligands 2a-c coordinate in a tridentate fashion forming chelate complexes MCl2(AQPNN-R) M = Co(ii) (6-8), and, for 2d, the Fe(ii) complex FeCl2(AQPNN-iPr) (9). A solution magnetic susceptibility value for 9 of 3.9μB is consistent with a monomer-dimer equilibrium. The synthesis of the dimeric complex [FeCl2(AQPNN-Ph)]2 (10) using 2a as well as solid state magnetic susceptibility measurements on 9 and 10 confirm this phenomenon. Ligand 3a coordinates to Fe(ii) in an interesting tetradentate fashion despite bearing a tertiary amine moiety giving octahedral FeCl2(P2NN') (11). All of the metal complexes have been characterized by elemental analysis, paramagnetic 1H NMR spectroscopy, solution magnetic susceptibility, and single crystal X-ray diffraction (XRD).