ChemInform Abstract: Metallacarboranes in Catalysis. Part 8. Catalytic Hydrogenolysis of Alkenyl Acetates. Catalytic Alkene Isomerization and Hydrogenation Revisited.
Abstract
The facile hydrogenolysis of alkenyl acetates such as isopropenyl- and 1-phenylvinyl-acetates with rhodacarborane catalyst precursors such as (I) and its 2,1,7- and 2,1,12-RhC2B9H11 analogues, to yield acetic acid and the corresponding alkenes is described by kinetic and deuterium-labeling investigations.
ChemInform Abstract
The facile hydrogenolysis of alkenyl acetates such as isopropenyl- and 1-phenylvinyl-acetates with rhodacarborane catalyst precursors such as (I) and its 2,1,7- and 2,1,12-RhC2B9H11 analogues, to yield acetic acid and the corresponding alkenes is described by kinetic and deuterium-labeling investigations. A reaction mechanism that is based upon the relatively slow formation and decomposition of a very reactive Rh(III) monohydride formed through the regioselective oxidative addition of Rh(I) in an exo-nido tautomer of the rhodacarborane to terminal B-H bonds is discussed. These results are devoted to a modification of previous proposals for the mechanisms of alkene isomerization and hydrogenation with rhodacarborane precursors.
