NN vs. NE (E = S or Se) coordination behavior of imino-phosphanamidinate chalcogenide ligands towards aluminum alkyls: efficient hydroboration catalysis of nitriles, alkynes, and alkenes
Dalton transactions (Cambridge, England : 2003)(2023)
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(R)P(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 (Bu-t), 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 [kappa(2)(NN)-{NHI(R)P(Ph)(E)N-Dipp}AlMe2] [R = Dipp, E = S (5a), Se (5b); R = Mes, E = S (6a), Se (6b)] or [kappa(2)(NE)-{NHI(R)P(Ph)(E)N-Dipp}AlMe2] [R = Bu-t, 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.
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Key words
efficient hydroboration catalysis,ligands,aluminum alkyls,alkynes,imino-phosphanamidinate
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