Diamagnetic molybdenum nitride complexes supported by diligating tripodal triamido-phosphine ligands as precursors to paramagnetic phosphine donors

摘要

The reaction of the ligand precursors P[CH2NHArR](3) (1a-c) with (Me2N)(3)Mo N generated the complexes P(CH2NArR)(3)Mo N (2a-c), where Ar-R = 3,5-(CH3)(2)C6H3 (a), Ph (b), and 3,5-(CF3)(2)C6H3 (c), with (Me2N)(3)Mo N generated the complexes P(CH2NArR)(3)Mo N (2a-c). Complex 2c was obtained in poor yield, due to the formation of P(CH2N-3,5-(CF3)(2)C6H3)(2)(CH2NH-3,5-(CF3)(2)C6H3)(NMe2H)(NMe2)Mo=N (3) as the major product. Reaction of 2a-b with VMes(3)THF generated the paramagnetic complexes P(CH2NArR)(3)Mo(mu-N) V(Mes) 3 (4a-b). The reaction of 2a-b with Ni(acac)(2) generated the Ni(0) complexes Ni[P(CH2NArR)(3)Mo N] 4 (5a-b) in poor yield. These complexes were synthesized in higher yields from the reaction of 2a-b with Ni(COD)(2), where COD = 1,5-cyclooctadiene. Reaction of either 5a with V(Mes)(3)THF or 4a with Ni(COD)(2) generated the paramagnetic nonanuclear complex Ni[P(CH2NArR)(3)Mo(mu-N) VMes(3)](4) (6a).