TITLE: Mechanistic Aspects of the Homogeneous Water Gas Shift Reaction.

AUTHOR: W. A. R. Slegeir;   R. S. Sapienza;   B. Easterling.

INST.  AUTHOR: Brookhaven National Lab., Upton, NY.

SPONSOR: Department of Energy, Washington, DC.

LANGUAGE: English

PUB.  TYPE: Technical Report

PUB.  COUNTRY: United States

SOURCE: Department of Energy [DE],  1980,  25p.

ABSTRACT:

Two reaction pathways for the homogeneous water gas shift reaction were found to be operative. An associative-type mechanism involving nucleophilic attack on a carbonyl ligand is indicated for ruthenium carbonyl complexes promoted by trimethylamine. This highly active system is favored by the dissociation of ruthenium clusters into mononuclear species. In contrast, Group VI metal carbonyl complexes demonstrate a dissociative mechanism, in which loss of a carbonyl ligand and formation of a formato complex are essential steps. An experiment, employing the technique of indirect photochemistry, is described to support this mechanism. These results provide a greater understanding of carbon oxide interactions in catalyst systems and of homogeneous analogues for heterogeneous reactions. (ERA citation 06:005125)

CONTRACT  NUMBER: AC02-76CH00016