26595-04-0Relevant academic research and scientific papers
Steric and Electronic Factors That Control Two-Electron Processes between Metal Carbonyl Cations and Anions
Zhen, Yueqian,Feighery, William G.,Lai, Chung-Kung,Atwood, Jim D.
, p. 7832 - 7837 (2007/10/02)
Reactions of metal carbonyl cations (Mn(CO)6(+), Re(CO)6(+), Mn(CO)5PPh3(+), Mn(CO)4(PPh3)2(+), Mn(CO)5PEt3(+), Mn(CO)5PPh2Me(+), Re(CO)5PPh3(+), and CpFe(CO)3(+)) with metal carbonyl anions (Co(CO)3PPh3(-), Co(CO)4(-), Mn(CO)5(-), Mn(CO)4PPh3(-), Mn(CO)4PEt3(-), Mn(CO)4PPh2Me(-), Mn(CO)3(PPh3)2(-), CpFe(CO)2(-), Re(CO)5(-), and Re(CO)4PPh3(-)) are reported.Peak potentials are reported for all ions, and nucleophilicites (as measured by reaction with MeI) are reported for the anions.Reaction of any metal carbonyl cation with any metal carbonyl anion leads ultimately to binuclear products, which are the thermodynamic products.The binuclear products are formed by single-electron transfer.In over half of the reactions between metal carbonyl cations and anions, a two-electron change results in a new metal carbonyl cation and anion.The two-electron change may be considered mechanistically as a CO(2+) transfer with the more nucleophilic of the two anions retaining the CO(2+).The kinetic and thermodynamic driving forces and the suggested mechanism are examined.
SYNTHESES AND CARBON MONOXIDE SUBSTITUTION REACTIONS OF η5-N-HETEROCYCLE MANGANESE TRICARBONYLS
Ji, Liang-Nian,Kershner, David L.,Rerek, Mark E.,Basolo, Fred
, p. 83 - 94 (2007/10/02)
A new method of synthesis of η5-pyrrolyltricarbonylmanganese(I) is reported, along with the first syntheses of η5-indolyltricarbonylmanganese(I) and of η5-1-pyrindinyltricarbonylmanganese(I).Kinetic studies on CO substitution reactions of these η5-N-heterocyclic manganese carbonyls show that the reactions take place by a second-order process, first-order in metal complex and first-order in nucleophile.The most significant observation is that the N-heterocyclic compounds react faster than do their carbocyclic counterparts.This anticipated result is consistent with the greater electron-withdrawing ability of the N systems in the transition state for reaction, because N is more electronegative than is C.
