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Title: Late transition metal. mu. -oxo and. mu. -imido complexes

Abstract

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.

Authors:
Publication Date:
Research Org.:
Missouri Univ., Columbia, MO (USA)
Sponsoring Org.:
DOE/ER
OSTI Identifier:
6332549
Report Number(s):
DOE/ER/13880-3
ON: DE91005349
DOE Contract Number:  
FG02-88ER13880
Resource Type:
Technical Report
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, 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

Citation Formats

Sharp, P R. Late transition metal. mu. -oxo and. mu. -imido complexes. United States: N. p., 1990. Web. doi:10.2172/6332549.
Sharp, P R. Late transition metal. mu. -oxo and. mu. -imido complexes. United States. doi:10.2172/6332549.
Sharp, P R. Mon . "Late transition metal. mu. -oxo and. mu. -imido complexes". United States. doi:10.2172/6332549. https://www.osti.gov/servlets/purl/6332549.
@article{osti_6332549,
title = {Late transition metal. mu. -oxo and. mu. -imido complexes},
author = {Sharp, P R},
abstractNote = {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.},
doi = {10.2172/6332549},
journal = {},
number = ,
volume = ,
place = {United States},
year = {1990},
month = {1}
}