Oxygen atom transfer between rhenium, sulfur, and phosphorus. Characterization and reactivity of Re(O)Cl/sub 3/(Me/sub 2/S)(OPPh/sub 3/) and Re(O)Cl/sub 3/(CNCMe/sub 3/)/sub 2/
Re(O)Cl/sub 3/(PPh/sub 3/)/sub 2/ (I) reacts with Me/sub 2/SO to form OPPh/sub 3/ and Re(O)Cl/sub 3/(Me/sub 2/S)(OPPh/sub 3/) (II), not Re(O)Cl/sub 3/(Me/sub 2/SO)(PPh/sub 3/) as had been previously reported. Compounds I and II are catalysts for oxygen atom transfer from Me/sub 2/SO to PPh/sub 3/. The mechanism of these oxygen atom transfer reactions has been studied with oxygen-18 labeling experiments. The rhenium oxo group does not appear to be involved; rather, the rhenium center acts as a Lewis acid activator for a Me/sub 2/SO ligand. The rhenium oxo group does, however, exchange oxygen atoms with Me/sub 2/S/sup 18/O, probably by a similar mechanism. Compound II is an excellent starting material for compounds of the form Re(O)Cl/sub 3/L/sub 2/, with L = isonitriles, phosphines, bipyridine, etc. The compounds Re(O)Cl/sub 3/-(CNR)/sub 2/ (R = CMe/sub 3/ (IV), CHMe/sub 2/, C/sub 6/H/sub 11/) are rare examples of high-valent isonitrile complexes. Data from an X-ray crystal structure of IV are reported. 36 references, 2 figures, 3 tables.
- Research Organization:
- Univ. of Washington, Seattle
- OSTI ID:
- 5648419
- Journal Information:
- Inorg. Chem.; (United States), Vol. 26:14
- Country of Publication:
- United States
- Language:
- English
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Related Subjects
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
CHLORIDES
CHEMICAL REACTIONS
ORGANIC PHOSPHORUS COMPOUNDS
ORGANIC SULFUR COMPOUNDS
RHENIUM COMPLEXES
EXPERIMENTAL DATA
LABELLED COMPOUNDS
OXYGEN 18
CHLORINE COMPOUNDS
COMPLEXES
DATA
EVEN-EVEN NUCLEI
HALIDES
HALOGEN COMPOUNDS
INFORMATION
ISOTOPES
LIGHT NUCLEI
NUCLEI
NUMERICAL DATA
ORGANIC COMPOUNDS
OXYGEN ISOTOPES
STABLE ISOTOPES
TRANSITION ELEMENT COMPLEXES
400201* - Chemical & Physicochemical Properties
400202 - Isotope Effects
Isotope Exchange
& Isotope Separation