title: Metal Complexes of Mesitylphosphine: Synthesis, Structure, and Spectroscopy.
abstract: A series of primary phosphine homoleptic complexes [ML(4)](n)()(+)X(n)() (1, M = Ni, n = 0; 2, M = Pd, n = 2, X = BF(4); 3, M = Cu, n = 1, X = PF(6); 4, M = Ag, n = 1, X = BF(4); L = PH(2)Mes, Mes = 2,4,6-Me(3)C(6)H(2)] was prepared from mesitylphosphine and Ni(COD)(2), [Pd(NCMe)(4)][BF(4)](2), [Cu(NCMe)(4)]PF(6), and AgBF(4), respectively. Reactions of 1-4 with MeC(CH(2)PPh(2))(3) (triphos) or [P(CH(2)CH(2)PPh(2))(3)] (tetraphos) afforded the derivatives [M(L')L](n)()(+)X(n)() (L' = triphos; 6, M = Ni, n = 0; 7, M = Cu, n = 1, X = PF(6); 8, M = Ag, n = 1, X = BF(4); L' = tetraphos; 9, M = Pd, n = 2, X = BF(4)). Addition of NOBF(4) to 1 yielded the nitrosyl compound [NiL(3)(NO)]BF(4), 5. The solution structure and dynamics of 1-9 were studied by (31)P 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.
authors.affiliation: Department of Chemistry, University of Delaware, Newark, Delaware 19716.
authors.forename: Igor V.
authors.initials: IV
authors.lastname: Kourkine
authors.forename: Stanislav V.
authors.initials: SV
authors.lastname: Maslennikov
authors.forename: Robert
authors.initials: R
authors.lastname: Ditchfield
authors.forename: David S.
authors.initials: DS
authors.lastname: Glueck
authors.forename: Glenn P. A.
authors.initials: GP
authors.lastname: Yap
authors.forename: Louise M.
authors.initials: LM
authors.lastname: Liable-Sands
authors.forename: Arnold L.
authors.initials: AL
authors.lastname: Rheingold