870248-75-2Relevant academic research and scientific papers
Reductive nitrosylation and proton-assisted bridge splitting of a (μ-oxo)dimanganese(III) complex derived from a polypyridine ligand with one carboxamide group
Ghosh, Kaushik,Eroy-Reveles, Aura A.,Olmstead, Marilyn M.,Mascharak, Pradip K.
, p. 8469 - 8475 (2005)
Aerobic oxidation of the Mn(II) complex [Mn(Papy3)(H 2O)](ClO4) (1, PaPy3- is the anion of the designed ligand N,N-bis(2-pyridylmethyl)amine-N-ethyl-2-pyridine-2- carboxamide) in acetonitrile affords the (μ-oxo)dimanganese-(III) complex [(Mn(PaPy3))2(μ-O)](ClO4)2 (3) in high yield, The unsupported single oxo bridge between the two high-spin Mn(III) centers in 3 is readily cleaved upon addition of proton sources such as phenol, acetic acid, and benzole acid, and complexes of the type [Mn(PaPy 3)(L)](ClO4) (5, L = PhO-; 6, L = AcO -; 7, L = BzO-) are formed. The basicity of the bridge is evident by the fact that simple addition of methanol to a solution of 3 in acetonitrile affords the methoxide complex [Mn(PaPy3)(OMe)](CLO 4) (4). The structures of 3-5 and 7 have been determined. Passage of NO through a solution of 3 in acetonitrile produces the {Mn-NO}6 nitrosyl [Mn(PaPy3)-(NO)](CLO4) (2) via reductive nitrosylation. Complexes 4-7 also afford the {Mn-NO}6 nitrosyl 2 upon reaction with NO. In the latter case, the anionic O-based ligands (such as MeO- and PhO-) act as built-in bases and promote reductive nitrosylation of the Mn(III) complexes.
