Late transition metal. mu. -oxo and. mu. -imido complexes
The synthesis and reactions of late-transition-metal oxo and imido complexes was explored. The deprotonation of platinum(II) hydroxo complexes yielded new oxo complexes. Attempted deprotonation of Cp*Rh(III) hydroxo complexes did not give oxo complexes but complex mixtures probably resulting from reduction of the Rh(III) center. The reaction of Na/Hg with (Cp*RhCl{sub 2}){sub 2} gave the very reactive Rh(II) dimer, (Cp*RhCl){sub 2}. Rhodium(I) imido complexes with the bis(dimethylphosphino)methane ligand were prepared and found to be similar to the previously prepared bis(diphenylphosphino)methane complexes. Attempts to prepare bis(diphenylphosphino)methylamine, bis(diphenylphosphino)phenylamine, PMe{sub e} and NO{sup +} analogues were not successful. Attempts to prepare Cp*Rh(III) imido complexes resulted in amido complexes and reduction. Rhodium (III) tris(3.5-dimethylpyrazoyl)borate analogues are reduction resistant but have not yet yielded imido complexes. The first imido complexes of Au were prepared by treating a Au oxo complex with amines or isocyanates. Dimeric Cp*Rh dioxygen and nitrosobenzene complexes were prepared by insertion into the Rh-Rh bond of (Cp*RhCl){sub 2}. The dioxygen complex activates a C-H bond of the Cp* ligand on treatment with PMe{sub 3}. Imido and oxo complexes nitrene and oxygen atom transfer product in reactions with CO. A novel electrophilic ring addition was observed with sterically protected aryl imido complexes. 15 refs.
- Research Organization:
- Missouri Univ., Columbia, MO (USA)
- Sponsoring Organization:
- DOE/ER
- DOE Contract Number:
- FG02-88ER13880
- OSTI ID:
- 6332549
- Report Number(s):
- DOE/ER/13880-3; ON: DE91005349
- Country of Publication:
- United States
- Language:
- English
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Related Subjects
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
GOLD COMPLEXES
CHEMICAL PREPARATION
PLATINUM COMPLEXES
RHODIUM COMPLEXES
CARBON MONOXIDE
ION PAIRS
LEWIS BASES
NITROSO COMPOUNDS
NUCLEAR MAGNETIC RESONANCE
OXYGEN COMPLEXES
PROGRESS REPORT
SILVER COMPLEXES
STRUCTURAL CHEMICAL ANALYSIS
BASES
CARBON COMPOUNDS
CARBON OXIDES
CHALCOGENIDES
COMPLEXES
DOCUMENT TYPES
MAGNETIC RESONANCE
ORGANIC COMPOUNDS
ORGANIC NITROGEN COMPOUNDS
OXIDES
OXYGEN COMPOUNDS
RESONANCE
SYNTHESIS
TRANSITION ELEMENT COMPLEXES
400201* - Chemical & Physicochemical Properties