80512-13-6Relevant academic research and scientific papers
Manganese(0) radicals and the reduction of cationic carbonyl complexes: Selectivity in the ligand dissociation from 19-electron species
Kuchynka,Amatore,Kochi
, p. 4087 - 4097 (2008/10/08)
Products and stoichiometry for the cathodic reduction of the series of carbonylmanganese(I) cations Mn(CO)5L+, where L - CO, MeCN, pyridine, and various phosphines, derive from 1-electron transfer to generate the 19-electron radicals Mn(CO)5L? as reactive intermediates. The CO derivative Mn(CO)6+ affords mainly the anionic Mn(CO)5- by the facile ligand dissociation of Mn(CO)6? to the 17-electron radical Mn(CO)5? followed by reduction. The acetonitrile and pyridine derivatives Mn(CO)5NCMe+ and Mn(CO)5py+ produce high yields of the dimer Mn2(CO)10 by an unusual and highly selective heterolytic coupling of Mn(CO)5- and the reactant cation. Structural factors involved in the conversion of 19-electron radicals to their 17-electron counterparts are examined in the reduction of the graded series of phosphine derivatives Mn(CO)5P+, where P = triaryl- and trialkylphosphines. The formation of the hydridomanganese complexes HMn(CO)4P is ascribed to hydrogen atom transfer to the 19-electron radicals Mn(CO)5P? followed by extrusion of CO. The lability of carbonylmanganese radicals is underscored by rapid ligand substitution to afford the bis(phosphine) byproduct HMn(CO)3P2.
