Synthesis and reactivity of compounds containing ruthenium-carbon, -nitrogen, and -oxygen bonds

Technical Report · Sat Dec 01 04:00:00 EST 1990

DOI:https://doi.org/10.2172/5530662· OSTI ID:5530662

Hartwig, J F

The products and mechanisms of the thermal reactions of several complexes of the general structure (PMe{sub 3}){sub 4}Ru(X)(Y) and (DMPM){sub 2}Ru(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 (PMe{sub 3}){sub 4}Ru(Ph)(Me) or (PMe{sub 3}){sub 4}Ru(Ph){sub 2} leads to the ruthenium benzyne complex (PMe{sub 3}){sub 4}Ru({eta}{sup 2}-C{sub 6}H{sub 4}) (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 CO{sub 2} and hydrogenolysis. Mechanistic studies on these reactions are described. The generation of a series of reactive ruthenium complexes of the general formula (PMe{sub 3}){sub 4}Ru(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.

• Research Organization: Lawrence Berkeley Lab., CA (USA)
• Sponsoring Organization: DOE; USDOE, Washington, DC (USA)
• DOE Contract Number: AC03-76SF00098
• OSTI ID: 5530662
• Report Number(s): LBL-30200; ON: DE91014229
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400201* -- Chemical & Physicochemical Properties
BOND ANGLE
BOND LENGTHS
CHEMICAL ACTIVATION
CHEMICAL PREPARATION
CHEMICAL REACTIONS
COHERENT SCATTERING
COMPLEXES
DECOMPOSITION
DIFFRACTION
DIMENSIONS
LENGTH
NMR SPECTRA
ORGANIC COMPOUNDS
ORGANOMETALLIC COMPOUNDS
PYROLYSIS
RUTHENIUM COMPLEXES
SCATTERING
SPECTRA
STRUCTURAL CHEMICAL ANALYSIS
SYNTHESIS
THERMOCHEMICAL PROCESSES
TRANSITION ELEMENT COMPLEXES
X-RAY DIFFRACTION