http://www.loc.gov/mods/v3 http://www.loc.gov/standards/mods/v3/mods-3-2.xsd
Spectroscopic and catalytic investigation of organometallic processes incorporating CO and CO₂
Several FTIR techniques have been used to investigate C1 chemical processes. In situ high pressure FTIR spectroscopy was employed in the study of the homogeneously catalyzed production of alkyl formats from alcohols and carbon monoxide by transition metal alkoxides in the presence of alkali metal alkoxides. The similarity of the band patterns of the species present in the v(CO) IR spectrum necessitated the use of infrared band shape analysis to deconvolute the grossly overlapping band pattern. The catalytic intermediate identified in this way was an alkoxycarbonyl derivative which is protonated by alcohol to afford the alkyl formate product. Band shape analysis has also been applied to observe contact ion pairing in [Na][HFe(CO)3PPh3], and to follow the kinetic of CO2/CO insertion into MeW(CO)5-. Another spectral analysis technique, DNMR, has been used in a kinetic study of the the cis, trans isomerization of HCr(CO)4(13CO)-. The activation parameters suggest rearrangement via a trigonal twist mechanism involving a pseudopentacoordinate intermediate or transition state. Interest in the alkoxycarbonyl species has led to the study of the stable cobalt compound CH3OC(O)Co(CO)3PPh3. This species is a model for the many catalytic reactions which are proposed to involve an alkoxycarbonyl intermediate, and is catalytic itself in the production of dialkyl carbonates from CO in alcohols. Under mild conditions, an interaction between the alcohol protons and the unbound oxygen of the alkoxycarbonyl ligand is observed by FTIR spectroscopy. An investigation of the kinetics of carbonyl exchange reaction have also been performed. Another oxygen containing ligand, Ph2P(O)NPPh3, has been prepared from the reaction of [PPN][Cl] with NaOMe in methanol. The product of the reaction of the novel ligand with W(CO)5THF, W(CO)5OPPh2NPPH3, has been characterized by X-ray crystallography...
Includes bibliographical references (leaves 105-112).