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Comparisons of the physical and chemical properties of isomeric pairs. 2. Photochemical, thermal, and electrochemical cis-trans isomerizations of M(Ph/sub 2/PCH/sub 2/PPh/sub 2/)/sub 2/Cl/sub 2/ (M = Ru/sup II/, Os/sup II)

Journal Article · · Inorg. Chem.; (United States)
DOI:https://doi.org/10.1021/ic00133a033· OSTI ID:6307172

The complexes cis- and trans-Ru/sup II/(dppm)/sub 2/Cl/sub 2/ (dppm = Ph/sub 2/PCH/sub 2/PPh/sub 2/) have been found to undergo isomerization reactions induced by light, heat, or oxidation to Ru(III). The conversion trans ..-->.. cis occurs thermally while cis ..-->.. trans occurs photochemically apparently by irradiation of the lowest lying d-d transition. Upon chemical or electrochemical oxidation of the cis isomer, the trans isomer of Ru(III) forms quantitatively. The cis isomer was found to be substitution labile in solvents that can act as ligands while the trans isomer is inert. Comparisons of the three-pathway isomerization of Ru(dppm)/sub 2/Cl/sub 2/ are also made with its osmium analogue and with the carbonyl complex (N,N'-Me/sub 2/Im)/sub 2/W(CO)/sub 4/.

Research Organization:
Univ. of North Carolina, Chapel Hill
DOE Contract Number:
AS05-78ER06034
OSTI ID:
6307172
Journal Information:
Inorg. Chem.; (United States), Journal Name: Inorg. Chem.; (United States) Vol. 21:3; ISSN INOCA
Country of Publication:
United States
Language:
English