Diamagnetic molybdenum nitride complexes supported by diligating tripodal triamido-phosphine ligands as precursors to paramagnetic phosphine donors†
Abstract
The reaction of the ligand precursors P[CH2NHArR]3 (1a–c) with (Me2N)3MoN generated the complexes P(CH2NArR)3MoN (2a–c), where ArR = 3,5-(CH3)2C6H3 (a), Ph (b), and 3,5-(CF3)2C6H3 (c), with (Me2N)3MoN generated the complexes P(CH2NArR)3MoN (2a–c). Complex 2c was obtained in poor yield, due to the formation of P(CH2N-3,5-(CF3)2C6H3)2(CH2NH-3,5-(CF3)2C6H3)(NMe2H)(NMe2)MoN (3) as the major product. Reaction of 2a–b with VMes3THF generated the paramagnetic complexes P(CH2NArR)3Mo(μ-N)V(Mes)3 (4a–b). The reaction of 2a–b with Ni(acac)2 generated the Ni(0) complexes Ni[P(CH2NArR)3MoN]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)3THF or 4a with Ni(COD)2 generated the paramagnetic nonanuclear complex Ni[P(CH2NArR)3Mo(μ-N)VMes3]4 (6a).