A series of primary phosphine homoleptic complexes [ML4]n+Xn (1, M = Ni, n = 0; 2, M = Pd, n = 2, X = BF4; 3, M = Cu, n = 1, X = PF6; 4, M = Ag, n = 1, X = BF4; L = PH2Mes, Mes = 2,4,6-Me3,C6H2] was prepared from mesitylphosphine and Ni(COD)2, [Pd(NCMe)4][BF4]2, [Cu(NCMe)4]PF6, and AgBF4, respectively. Reactions of 1-4 with MeC(CH2PPh2)3 (triphos) or [P(CH2CH2PPh2)3] (tetraphos) afforded the derivatives [M(L')L]n+ Xn (L' = triphos; 6, M = Ni, n = 0; 7, M = Cu, n = 1, X = PF6; 8, M = Ag, n = 1, X = BF4; L' = tetraphos; 9, M = Pd, n = 2, X = BF4). Addition of NOBF4 to 1 yielded the nitrosyl compound [NiL3(NO)]BF4, 5. The solution structure and dynamics of 1-9 were studied by 31P NMR spectroscopy (including the first reported analyses of a 12-spin system for 1-2). Complexes 1,3,6, and 7·solvent were characterized crystallographically. The structural and spectroscopic studies suggest that the coordination properties of L are dominated by its relatively small cone angle and that the basicity of L is comparable to that of more commonly used tertiary phosphines.
ASJC Scopus subject areas
- Physical and Theoretical Chemistry
- Inorganic Chemistry