TY - JOUR
T1 - Mechanistic differences between "reductive" and "oxidative" heterolysis of metal-carbon G bonds
AU - Shaham, Nurit
AU - Cohen, Haim
AU - Van Eidik, Rudi
AU - Meyerstein, Dan
PY - 2000/12/1
Y1 - 2000/12/1
N2 - Volumes of activation, A V, for the heterolysis reactions of copper complexes with metal-carbon a bonds, rfc. [(H2O)5Cum-R]2t (R = CH2C(V or CHCV) and [LCuII-R]t (L = 2,5,8,1 l-tetramethyl-2,5,8,11-tetraazadodecane; R = CH2CO2~), were determined using high pressure pulse-radiolysis techniques. In addition, the volume of activation for the bimolecular decomposition of [LCun-CHj]+ was determined. The results reveal the different roles of the solvent (water) in the transition states for oxidative and reductive heterolysis reactions.
AB - Volumes of activation, A V, for the heterolysis reactions of copper complexes with metal-carbon a bonds, rfc. [(H2O)5Cum-R]2t (R = CH2C(V or CHCV) and [LCuII-R]t (L = 2,5,8,1 l-tetramethyl-2,5,8,11-tetraazadodecane; R = CH2CO2~), were determined using high pressure pulse-radiolysis techniques. In addition, the volume of activation for the bimolecular decomposition of [LCun-CHj]+ was determined. The results reveal the different roles of the solvent (water) in the transition states for oxidative and reductive heterolysis reactions.
UR - http://www.scopus.com/inward/record.url?scp=3142761170&partnerID=8YFLogxK
U2 - 10.1039/b003347m
DO - 10.1039/b003347m
M3 - Article
AN - SCOPUS:3142761170
SN - 1470-479X
SP - 3356
EP - 3359
JO - Journal of the Chemical Society. Dalton Transactions
JF - Journal of the Chemical Society. Dalton Transactions
IS - 19
ER -