N^N vs. N^E (E = S or Se) coordination behavior of imino-phosphanamidinate chalcogenide ligands towards aluminum alkyls: efficient hydroboration catalysis of nitriles, alkynes, and alkenes

Abstract

The synthesis, characterization, and catalytic application of six aluminum alkyl complexes supported by various imino-phosphanamidinate chalcogenide ligands are described. Six different unsymmetrical imino-phosphanamidinate chalcogenide ligands [NHI^RP(Ph)(E)NH-Dipp] [R = 2,6-diisopropylphenyl (Dipp), E = S (2a-H), Se (2b-H); R = mesityl (Mes), E = S (3a-H), Se (3b-H); R = tert-butyl (^tBu), E = S (4a-H), Se (4b-H)] were prepared by the oxidation of respective imino-phosphanamide ligands (1a, 1b and 1c) with elemental chalcogen atoms (S and Se). The aluminum complexes with imino-phosphanamidinate chalcogenide ligands with the general formulae [κ²_NN-{NHI^RP(Ph)(E)N-Dipp}AlMe₂] [R = Dipp, E = S (5a), Se (5b); R = Mes, E = S (6a), Se (6b)] or [κ²_NE-{NHI^RP(Ph)(E)N-Dipp}AlMe₂] [R = ^tBu, E = S (7a), Se (7b)] were synthesized in good yields from the reaction of the suitable protic ligands (2a,b-H–4a,b-H) and trimethylaluminum in a 1 : 1 molar ratio in toluene at room temperature. All the protic ligands and aluminum complexes were well characterized by multi-nuclear NMR spectroscopy, and the solid-state structures of 2a,b-H–4a,b-H, 5a,b–6a,b and 7b are established by single crystal X-ray diffraction analysis. The aluminum complexes 5a,b–7a,b were tested as catalysts for the hydroboration of nitriles, alkynes, and alkenes under mild conditions. The catalytic hydroboration reactions of nitriles, alkynes, and alkenes were accomplished with complex 5b at a mild temperature under solvent-free conditions to afford a high yield of the corresponding N,N-diborylamines, vinylboranes and alkyl boronate esters, respectively.