37685-57-7

Upstream product

• 1486-28-8 diphenyl(methyl)phosphine 

Downstream Products

• 119747-58-9 CH₃C₅H₄Mn(CO)PCH₃(C₆H₅)2CC(CH₃)2 
• 119747-59-0 CH₃C₅H₄Mn(CO)PCH₃(C₆H₅)2CC(C₆H₅)2 

Relevant academic research and scientific papers

Kinetics, Thermodynamics, and Mechanism of the Radical Chain Process for Ligand Substitution of Metal Carbonyls

The radical chain process for the ligand substitution of a variety of carbonylmanganese derivatives (MnL) can be induced chemically or electrochemically with turnover numbers that can exceed 103.The catalytic cycle is initiated by electron transfer to afford the 17-electron carbonylmanganese cation MnL+.The propagation steps in the chain process are (1) the facile ligand exchange of MnL+ with the added nucleophile L to afford MnL+ followed by (2) the reduction of MnL+ by a homogeneous process involving cross electron exchange with MnL and/or heterogeneous electron transfer at the electrode.This carbonylmetal system is sufficiently well-behaved to allow the kinetics and thermodynamics for each step of the catalytic cycle to be examined in quantitative detail by transient and bulk electrochemical techniques.Analysis of the reversible cyclic voltammograms of MnL, both in the presence and in the absence of the nucleophile L, is achieved by Feldberg's digital simulation method.The computer simulation of the experimental cyclic voltammograms provides accurate values of the second-order rate constants for the rapid ligand exchange of MnL+ with a variety of added nucleophiles L.The unusual reactivity patterns for substitution in the paramagnetic MnL are presented in the context of previous studies with other metal carbonyls.

ELECTRON TRANSFER AND TRANSIENT RADICALS IN ORGANOMETALLIC CHEMISTRY

The variety of reactions available with metal carbonyls, both as mononuclear species and polynuclear clusters, is used to underscore the importance of electron transfer, transient radicals and ion radicals in organometallic chemistry.

STERIC AND ELECTRONIC EFFECTS IN LIGAND SUBSTITUTION OF METAL CARBONYLS. RAPID KINETICS OF LABILE CARBONYLMANGANESE COMPLEXES BY TRANSIENT ELECTROCHEMICAL TECHNIQUES.

The ligand substitution kinetics of a series of carbonylmanganese cations MeCpMn(CO)//2L** plus with L equals 3- and 4-substituted pyridine ligands are measured for a variety of phosphine nucleophiles N of differing steric and electronic properties. The unified free energy relationship is shown for the first time to accommodate all the extensive rate data, if the steric effect is evaluated by Tolman's cone angles for the phosphines, and the electronic effects are evluated by the acid-base dissociation constants of the pyridine ligands and the phosphine nucleophiles. The range of second-order rate constants k//1 for ligand substitution of MeCpMn(CO)//2L** plus extends over four decades from 3. 0 to 2 multiplied by 10**4 M** minus **1 s** minus **1. The mechanism of ligand substitution of metal carbonyls is central to the successful catalysis of a variety of important processes leading to the reduction of carbon monoxide.