Molybdenum Hydride and Dihydride Complexes Bearing Diphosphine Ligands with a Pendant Amine: Formation of Complexes...

CpMo(CO)(PNP)H complexes (PNP = (R2PCH2)2NMe, R = Et or Ph) were synthesized by displacement of two CO ligands of CpMo(CO)3H by the PNP ligand; these complexes were characterized by IR and variable temperature (1)H and (31)P NMR spectroscopy. CpMo(CO)(PNP)H complexes are formed as mixture of cis- and trans-isomers. The structures of both cis-CpMo(CO)(P(Et)N(Me)P(Et))H and trans-CpMo(CO)(P(Ph)N(Me)P(Ph))H were determined by single crystal X-ray diffraction. Electrochemical oxidation of CpMo(CO)(P(Et)N(Me)P(Et))H and CpMo(CO)(P(Ph)N(Me)P(Ph))H in CH3CN are both irreversible at slow scan rates and quasireversible at higher scan rates, with E1/2 = -0.36 V (vs Cp2Fe(+/0)) for CpMo(CO)(P(Et)N(Me)P(Et))H and E1/2 = -0.18 V for CpMo(CO)(P(Ph)N(Me)P(Ph))H. Hydride abstraction from CpMo(CO)(PNP)H with [Ph3C](+)[A](-) (A = B(C6F5)4 or BAr(F)4; [Ar(F) = 3,5-bis(trifluoromethyl)phenyl]) afforded "tuck-in" [CpMo(CO)(κ(3)-PNP)](+) complexes that feature the amine bound to the metal. Displacement of the κ(3) Mo-N bond by CD3CN gives [CpMo(CO)(PNP)(CD3CN)](+). The kinetics of this reaction were studied by (31)P{(1)H} NMR spectroscopy for [CpMo(CO)(κ(3)-P(Et)N(Me)P(Et))](+), providing the activation parameters ΔH(⧧) = 21.6 ± 2.8 kcal/mol, ΔS(⧧) = -0.3 ± 9.8 cal/(mol K), Ea = 22.1 ± 2.8 kcal/mol. Protonation of CpMo(CO)(P(Et)N(Me)P(Et))H affords the Mo dihydride complex [CpMo(CO)(κ(2)-P(Et)N(Me)P(Et))(H)2](+), which loses H2 to generate [CpMo(CO)(κ(3)-P(Et)N(Me)P(Et))](+) at room temperature. Our results show that the pendant amine has a strong driving force to form stable "tuck-in" [CpMo(CO)(κ(3)-PNP)](+) complexes, and also promotes hydrogen elimination from [CpMo(CO)(PNP)(H)2](+) complexes by formation of a Mo-N dative bond. CpMo(CO)(dppp)H (dppp = 1,3-bis(diphenylphosphino)propane) was studied as a Mo diphosphine analogue without a pendant amine, and the product of protonation of this complex gives [CpMo(CO)(dppp)(H)2](+).