Anionic and Mononuclear Phosphinidene and Imide Complexes of Niobium

作者：Searles Keith; Carroll Patrick J; Mindiola Daniel J^*

来源：Organometallics, 2015, 34(19): 4641-4643.

DOI：10.1021/acs.organomet.5b00518

The reactivity of a terminal methylidene complex of niobium, [(ArO)(2)Nb=CH2(CH3)(CH2PPh3)] (1), with the primary phosphine PhPH2 results in formation of the anionic phosphinidene complex [H3CPPh3][(ArO)(2)Nb=PPh(CH3)(2)] (2), where both the methylidene and ylide ligands of the precursor experience protonation. Multinuclear NMR spectroscopy and X-ray diffraction studies indicate formation of a bent phosphinidene ligand Similar reactivity is also observed with primary amines, specifically AdNH(2) (Ad = 1-adamantyl) and MesNH(2) (Mes = 2,4,6-trimethylphenyl), resulting in formation of the corresponding imide complexes [H3CPPh3][(ArO)(2)Nb=NR(CH3)(2)] (R = Mes, (3), Ad, (4)). Whereas 2 has a bent phosphinidene ligand and pseudo trigonal bipyramidal structure, the solid-state structure determination of complex 4 reveals a linear imide ligand and square-pyramidal geometry, where the imide enjoys significant Nb-NR multiple-bond character.

• 出版日期2015-10-12