Donald Eugene Morris

Mechanistic Pathways in the Catalysis of Olefin Hydrocarboxylation by Rhodium, Iridium, and Cobalt Complexes

Abstract Carboxylic acids can be synthesized by reacting olefins with carbon monoxide and water in the presence of a variety of transition transition metal catalysts: (1) Metals which have been employed as catalysts for this reaction include nickel, as first reported [1] by Reppe for the synthesis of acrylic and propionic acids from acetylene and ethylene, cobalt, iron, rhodium, ruthenium, palladium, and platinum [2]. The earlier studies of this reaction employed nickel, cobalt, and iron catalysts and required rather severe operating conditions, viz., 200-300 atm and 200-300°C. More recently the use of rhodium [3], iridium [4], platinum [5], palladium [6], and pyridine-promoted cobalt [7] catalysts has been reported. These latter systems all function at relatively mild reaction conditions (see Table 1).

High Pressure, High Temperature Infrared‐Ultraviolet‐Visible Spectrophotometer Cell for in situ Catalyst Studies

An ir and uv‐visible spectrophotometer cell for recording the spectra of solutions at elevated temperatures and pressures has been designed and fabricated. The cell is used for characterization of reactive catalyst species and reaction intermediates which exist only at conditions above ambient. The temperature and pressure maxima are limited by the window material which, in turn, is determined by the spectral range to be examined. Large windows, variable path length, and relatively compact design permit the use of the cell interchangeably among a variety of commerically available ir and uv‐visible spectrophotometers without the need for special instrument modifications. The cell with CaF2 windows has been applied to studies of catalyst solutions at reaction conditions up to 100 atm at 200° C without any suggestion of window or cell failure. The design and construction of the cell are reported.

In situ high-pressure, high-temperature spectrophotometric studies of the chlorocarbonylbis(triphenylphosphine)rhodium(I) hydroformylation catalyst activated by hydroperoxides

Abstract The rate of hydroformylation of olefins catalyzed by RhCICO(Ph 3 P) 2 (I) is accelerated by the addition of a small amount of cyclohexenyl hydroperoxide which converts I into cis -RhCl(CO) 2 Ph 3 P (II), a very active olefin-hydroformylation and -isomerization catalyst.

Infrared investigation of the reactions of rhodiumcarbonyl halides and carbon monoxide at elevated pressures

Abstract Infrared spectral results at elevated carbon monoxide pressures suggest that rhodiumdicarbonyl halides and carbon monoxide exist in an equilibrium with the corresponding rhodiumtricarbonyl halides.

High-Pressure, High-Temperature Spectrophotometer Cell for in Situ Catalyst Identification

A high-pressure, high-temperature spectrophotometer cell has been designed and constructed in order to examine reacting solutions at conditions which are above ambient temperature and pressure. Large windows, a variable-path length, and a relatively compact design provide considerable versatility and permit the use of the cell interchangeably among a variety of commercially available IR and UV-Visible spectrophotometers without the need for special instrument modification. The cell has been used to study solutions at a variety of reaction conditions up to 100 atmospheres of pressure at 200°C without any suggestion of window or cell failure. The design and fabrication of the cell are reported. In addition, specific applications of the cell to studies of the rhodium-catalyzed hydroformylation of olefins are described.