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Title: 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)

Abstract

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/.

Authors:
;
Publication Date:
Research Org.:
Univ. of North Carolina, Chapel Hill
OSTI Identifier:
6307172
DOE Contract Number:  
AS05-78ER06034
Resource Type:
Journal Article
Journal Name:
Inorg. Chem.; (United States)
Additional Journal Information:
Journal Volume: 21:3
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; COMPLEXES; CHEMICAL PROPERTIES; ISOMERIZATION; PHYSICAL PROPERTIES; HETEROCYCLIC COMPOUNDS; ORGANIC PHOSPHORUS COMPOUNDS; ORGANOMETALLIC COMPOUNDS; OSMIUM CHLORIDES; RUTHENIUM CHLORIDES; EXPERIMENTAL DATA; CHEMICAL REACTIONS; CHLORIDES; CHLORINE COMPOUNDS; DATA; HALIDES; HALOGEN COMPOUNDS; INFORMATION; NUMERICAL DATA; ORGANIC COMPOUNDS; OSMIUM COMPOUNDS; REFRACTORY METAL COMPOUNDS; RUTHENIUM COMPOUNDS; TRANSITION ELEMENT COMPOUNDS; 400201* - Chemical & Physicochemical Properties; 400301 - Organic Chemistry- Chemical & Physicochemical Properties- (-1987)

Citation Formats

Sullivan, B P, and Meyer, T J. 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). United States: N. p., 1982. Web. doi:10.1021/ic00133a033.
Sullivan, B P, & Meyer, T J. 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). United States. https://doi.org/10.1021/ic00133a033
Sullivan, B P, and Meyer, T J. Fri . "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)". United States. https://doi.org/10.1021/ic00133a033.
@article{osti_6307172,
title = {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)},
author = {Sullivan, B P and Meyer, T J},
abstractNote = {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/.},
doi = {10.1021/ic00133a033},
url = {https://www.osti.gov/biblio/6307172}, journal = {Inorg. Chem.; (United States)},
number = ,
volume = 21:3,
place = {United States},
year = {1982},
month = {1}
}