High-spin manganese(II) complexes of an amido/bis(phosphine) PNP ligand.
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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. Reduction of 6 in the presence of pyridine produced material analytically consistent with (PNP)Mn(py)(3) (8), whereas reduction in the presence of 2,2'-bipyridine gave fully characterized (PNP)Mn(bipy) (9). Compounds 5 and 7 display magnetic moments indicative of high-spin Mn(II) (S = 5/2). The magnetic moment of 9 (S = 2) was interpreted as an antiferromagnetic combination of a high-spin Mn(II) center and a singly reduced bipyridine ligand. Addition of a single CO ligand to 9 generated diamagnetic, low-spin (PNP)Mn(bipy)(CO) (10). Solid-state structures of 5, 7, 9, and 10 were determined by X-ray diffraction methods and used in conjunction with density functional theory studies to analyze the electronic nature of the (PNP)Mn complexes under study.
author list (cited authors)
Bacciu, D., Chen, C., Surawatanawong, P., Foxman, B. M., & Ozerov, O. V.
complete list of authors
Bacciu, Deborha||Chen, Chun-Hsing||Surawatanawong, Panida||Foxman, Bruce M||Ozerov, Oleg V