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[CH₂NHAr^R]₃ (1a–c) with (Me₂N)₃MoN generated the complexes P(CH₂NAr^R)₃MoN (2a–c), where Ar^R = 3,5-(CH₃)₂C₆H₃ (a), Ph (b), and 3,5-(CF₃)₂C₆H₃ (c), with (Me₂N)₃MoN generated the complexes P(CH₂NAr^R)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(CH₂NAr^R)₃Mo(μ-N)V(Mes)₃ (4a–b). The reaction of 2a–b with Ni(acac)₂ generated the Ni(0) complexes Ni[P(CH₂NAr^R)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(CH₂NAr^R)₃Mo(μ-N)VMes₃]₄ (6a).