84180-15-4Relevant academic research and scientific papers
ELECTROOXIDATION OF METAL CARBONYL ANIONS. FORMATION AND REACTIVITY OF 17-ELECTRON MANGANESE(0) RADICALS
Kuchynka, D. J.,Amatore, C.,Kochi, J. K.
, p. 133 - 154 (2007/10/02)
The series of carbonylmanganese anions Mn(CO)3P2-, with P = phosphites and phosphines, undergo reversible anodic oxidation to the 17-electron radicals Mn(CO)3P2. in tetrahydrofuran solutions.The reactivity of the carbonyl-manganese radicals of Mn(CO)3P2. is evaluated in the context of hydrogen atom transfer from tributyltin hydride.The donor properties of the carbonylmanganates are strongly modulated by the ligands - the reversible oxidation potentials E1/2 of phosphine-substituted anions being significantly more negative than those of the phosphite analogs.By contrast the reactivity of the phosphine- and phosphite-substituted radicals are not differentiated by electronic factors.However steric effects (as indicated by the cone angle of the phosphite or phosphine ligand play a strong role in determining the reactivity of these 17-electron radicals.The combination of cyclic voltammetry, chronoamperometry, coulometry, and product analysis is used to establish the mechanism of hydrogen transfer from tribultyn hydride to Mn(CO)3P2. in THF solutions.The measurement of the second-order rate constants k2 for hydrogen transfer by double potential step chronoamperometry (DPSC) is described.
Synthesis of Cationic Mer-Phosphite-Substituted Carbonylmanganese Compounds
Berke, Heinz,Weiler, Gertrud
, p. 431 - 437 (2007/10/02)
Di-, tri- and tetrasubstituted carbonylmanganese compounds (OC)nL6-nMn(+)PF6(-) (L = P(OMe)3, P(OEt)3, P(O-i-Pr)3, P(OPh)3 and P(O-o-Tolyl)3) are synthesized by hydride abstraction and substitution processes from corresponding hydridemanganese compounds. - Key words: Phosphite Substitution, Carbonylmanganese Cations, Hydride Abstraction
