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Synthesis and reactivity of compounds containing ruthenium-carbon, -nitrogen, and -oxygen bonds [electronic resource].

Published
Washington, D.C. : United States. Dept. of Energy, 1990.
Oak Ridge, Tenn. : Distributed by the Office of Scientific and Technical Information, U.S. Dept. of Energy.
Physical Description
Pages: (417 pages) : digital, PDF file
Additional Creators
Lawrence Berkeley National Laboratory, United States. Department of Energy, and United States. Department of Energy. Office of Scientific and Technical Information
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Summary
The products and mechanisms of the thermal reactions of several complexes of the general structure (PMe₃)₄Ru(X)(Y) and (DMPM)₂Ru(X)(Y) where X and Y are hydride, aryl, and benzyl groups, have been investigated. The mechanism of decomposition depends critically on the structure of the complex and the medium in which the thermolysis is carried out. The alkyl hydride complexes are do not react with alkane solvent, but undergo C-H activation processes with aromatic solvents by several different mechanisms. Thermolysis of (PMe₃)₄Ru(Ph)(Me) or (PMe₃)₄Ru(Ph)₂ leads to the ruthenium benzyne complex (PMe₃)₄Ru(η²-C₆H₄) (1) by a mechanism which involves reversible dissociation of phosphine. In many ways its chemistry is analogous to that of early rather than late organo transition metal complexes. The synthesis, structure, variable temperature NMR spectroscopy and reactivity of ruthenium complexes containing aryloxide or arylamide ligands are reported. These complexes undergo cleavage of a P-C bond in coordinated trimethylphosphine, insertion of CO and CO₂ and hydrogenolysis. Mechanistic studies on these reactions are described. The generation of a series of reactive ruthenium complexes of the general formula (PMe₃)₄Ru(R)(enolate) is reported. Most of these enolates have been shown to bind to the ruthenium center through the oxygen atom. Two of the enolate complexes 8 and 9 exist in equilibrium between the O- and C-bound forms. The reactions of these compounds are reported, including reactions to form oxygen-containing metallacycles. The structure and reactivity of these ruthenium metallacycles is reported, including their thermal chemistry and reactivity toward protic acids, electrophiles, carbon monoxide, hydrogen and trimethylsilane. 243 refs., 10 tabs.
Report Numbers
E 1.99:lbl-30200
lbl-30200
Subject(s)
Other Subject(s)
Note
Published through SciTech Connect.
12/01/1990.
"lbl-30200"
"DE91014229"
Hartwig, J.F.
Funding Information
AC03-76SF00098
View MARC record | catkey: 14396353