Stabilization of Cp(CO)2Mn fragment radicals?
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Angewandte Chemie 97 (10): 869--870 (1985)

The neutral complexes Cp1(CO)2MnL (Cp1 = methylcyclopentadienyl; L = 4-cyanopyridine, p-(NC)2C6H4) and Cp1(CO)2Mn2L1 (L1 = 4,4'-bipyridine) were reduced by K to give ligand-centered radical anionic complexes Cp1(CO)2Mn(L-.bul.) (I; L = 4-cyanopyridine) and Cp1(CO)2Mn2L2.bul.- (II; L2 = p-(NC)2C6H4, 4,4'-bipyridine). The ESR spectra of paramagnetic I and II showed they contained neutral Mn(I) fragments, in which the d6 Mn stabilized the radical anionic ligands by p-backbonding. In contrast, neutral, paramagnetic Cp1(CO)2MnR (R = NHC6H4NMe2-4, imidazolo, NHR1; R1 = 4-pyridyl) and Cp5(CO)2Mn(NHC6H4Me-4) (Cp5 = pentamethylcyclopentadienyl), prepd. by oxidative deprotonation of Cp1(CO)2Mn(RH) or Cp5(CO)2Mn(NH2C6H4Me-4), contained low spin Mn(II) and diamagnetic ligands. on SciFinder(R)
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