TY - JOUR
T1 - Electrochemical Investigations of Isomerism in Manganese and Group (VI) Dicarbonylbis [1,2-bis(diphenylphosphino)ethane] Complexes
AU - Wimmer, F. L.
AU - Snow, M. R.
AU - Bond, A. M.
PY - 1974/7/1
Y1 - 1974/7/1
N2 - A series of complexes of the general formula [M(CO)2(DPE)2]0,+,2+ is known (M = Mn, Cr, Mo, W; DPE = 1,2-bis(diphenylphosphino) ethane). In addition to existing in several oxidation states, some of the complexes have been isolated in cis and trans isomeric forms. Electrochemical investigations at mercury and platinum electrodes in acetone, dichloromethane, and nitromethane have given a wide variety of new synthetic, kinetic, and thermodynamic data on the complexes. The electrochemistry of the different oxidation states and isomeric forms is remarkably different and a highly specific technique for studying these complexes has been obtained. Strong evidence for the existence of the new complexes cis-[Cr(CO)2(DPE)2], trans-[Cr(CO)2(DPE)2]2+, trans-Mo(CO)2(DPE)2, and trans-W(CO)2(DPE)2 and other complexes is presented. Evidence for the existence of cis-[M(CO)2(DPE)2]+ (M = Cr, Mo, W) isomers in forms that are readily isomerized to the trans isomer has also been obtained. These complexes are stabilized considerably at low temperature. All thermodynamic data obtained are in accord with the known chemistry of the compounds. In oxidation state II, there is no evidence for stable cis isomers, while six-coordinate trans species decrease in kinetic stability in the order Cr > (Mo≃ W).
AB - A series of complexes of the general formula [M(CO)2(DPE)2]0,+,2+ is known (M = Mn, Cr, Mo, W; DPE = 1,2-bis(diphenylphosphino) ethane). In addition to existing in several oxidation states, some of the complexes have been isolated in cis and trans isomeric forms. Electrochemical investigations at mercury and platinum electrodes in acetone, dichloromethane, and nitromethane have given a wide variety of new synthetic, kinetic, and thermodynamic data on the complexes. The electrochemistry of the different oxidation states and isomeric forms is remarkably different and a highly specific technique for studying these complexes has been obtained. Strong evidence for the existence of the new complexes cis-[Cr(CO)2(DPE)2], trans-[Cr(CO)2(DPE)2]2+, trans-Mo(CO)2(DPE)2, and trans-W(CO)2(DPE)2 and other complexes is presented. Evidence for the existence of cis-[M(CO)2(DPE)2]+ (M = Cr, Mo, W) isomers in forms that are readily isomerized to the trans isomer has also been obtained. These complexes are stabilized considerably at low temperature. All thermodynamic data obtained are in accord with the known chemistry of the compounds. In oxidation state II, there is no evidence for stable cis isomers, while six-coordinate trans species decrease in kinetic stability in the order Cr > (Mo≃ W).
UR - http://www.scopus.com/inward/record.url?scp=0000791645&partnerID=8YFLogxK
U2 - 10.1021/ic50137a015
DO - 10.1021/ic50137a015
M3 - Article
AN - SCOPUS:0000791645
SN - 0020-1669
VL - 13
SP - 1617
EP - 1623
JO - Inorganic Chemistry
JF - Inorganic Chemistry
IS - 7
ER -