Kinetic and thermodynamic stabilities of the geometric isomers of (R/sub 3/P)/sub 2/Ru(CO)/sub 2/Cl/sub 2/ and (R/sub 3/P)/sub 3/Ru(CO)Cl/sub 2/ complexes
A series of ruthenium(II) complexes of the type RuCl/sub 2/(CO)/sub 2/P/sub 2/ (P = Bzl/sub 3/P, Ph/sub 3/P, Ph/sub 2/MeP, PhMe/sub 2/P, Me/sub 3/P) have been prepared and characterized by elemental analyses, physical properties, infrared spectroscopy, uv-visible spectroscopy, and /sup 1/H, /sup 13/C(/sup 1/H) and /sup 31/P(/sup 1/H) NMR spectroscopy. The first-formed complex, with all ligand pairs trans(ttt), thermally isomerizes in solution to produce the isomer with all ligand pairs cis (ccc). This ccc isomer further isomerizes in solution to produce the thermodynamically preferred isomer with only the phosphine ligands trans (cct). The size and basicity of the phosphine affect the isomerization rate, which increases with an increase in size and a decrease in phosphine basicity and proceeds by initial dissociation of carbon monoxide. Activation and crystal parameters for the complex are reported. The bond distance of the phosphine trans to carbon monoxide in the trans isomer (d(RuP) = 2.490 (4) /angstrom/) is longer than the other two Ru-P distances (2.403 (4) /angstrom/). The /sup 31/P(H)NMR data also suggest that this phosphine is relatively weakly bound and so this phosphine likely dissociates as the first step in the geometric isomerization. 47 refs., 11 figs., 21 tabs.
- Research Organization:
- Univ. of Nevada, Reno (USA)
- OSTI ID:
- 5974248
- Journal Information:
- Inorg. Chem.; (United States), Vol. 27:23
- Country of Publication:
- United States
- Language:
- English
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Related Subjects
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
CARBONYLS
THERMODYNAMIC PROPERTIES
CHLORIDES
ORGANIC PHOSPHORUS COMPOUNDS
RUTHENIUM COMPLEXES
CARBON 13
CHEMICAL REACTION KINETICS
EXPERIMENTAL DATA
NMR SPECTRA
PHOSPHORUS 31
PROTONS
BARYONS
CARBON ISOTOPES
CHLORINE COMPOUNDS
COMPLEXES
DATA
ELEMENTARY PARTICLES
EVEN-ODD NUCLEI
FERMIONS
HADRONS
HALIDES
HALOGEN COMPOUNDS
INFORMATION
ISOTOPES
KINETICS
LIGHT NUCLEI
NUCLEI
NUCLEONS
NUMERICAL DATA
ODD-EVEN NUCLEI
ORGANIC COMPOUNDS
PHOSPHORUS ISOTOPES
PHYSICAL PROPERTIES
REACTION KINETICS
SPECTRA
STABLE ISOTOPES
TRANSITION ELEMENT COMPLEXES
400201* - Chemical & Physicochemical Properties
400202 - Isotope Effects
Isotope Exchange
& Isotope Separation