High-spin manganese(II) complexes of an amido/bis(phosphine) PNP ligand.

Syntheses of several Mn complexes supported by a monoanionic amido/bis(phosphino) PNP ligand (PNP = [2-P(CHMe(2))(2)-4-MeC(6)H(3)](2)N) from anhydrous MnCl(2) are reported. Treatment of (PNP)Li (2) with MnCl(2) in tetrahydrofuran (THF) led to isolation of either (PNP)Mn(mu-Cl)(2)Li(THF)(2) (5) or (PNP)MnCl (6), depending on the workup. Reaction of 6 with 2 equiv of MeLi resulted in isolation of (PNP)Mn(mu-Me)(2)Li(THF)(2) (7) that is structurally similar to 5.

Ligand reactivity in diarylamido/bis(phosphine) PNP complexes of Mn(CO)3 and Re(CO)3.

The syntheses of meridionally ligated tricarbonyl complexes (PNP)Mn(CO)(3) and (PNP)Re(CO)(3) are described (PNP = [2-P(CHMe(2))(2)-4-MeC(6)H(3)](2)N(-)). Cyclic voltammograms show reversible one-electron redox couples for both parent compounds (-0.34 V vs Cp(2)Fe(0/+) for (PNP)Mn(CO)(3), -0.