title: Interception and characterization of catalyst species in rhodium bis(diazaphospholane)-catalyzed hydroformylation of octene, vinyl acetate, allyl cyanide, and 1-phenyl-1,3-butadiene.
abstract: In the absence of H2, reaction of [Rh(H) (CO)2(BDP)] [BDP = bis(diazaphospholane)] with hydroformylation substrates vinyl acetate, allyl cyanide, 1-octene, and trans-1-phenyl-1,3-butadiene at low temperatures and pressures with passive mixing enables detailed NMR spectroscopic characterization of rhodium acyl and, in some cases, alkyl complexes of these substrates. For trans-1-phenyl-1,3-butadiene, the stable alkyl complex is an η(3)-allyl complex. Five-coordinate acyl dicarbonyl complexes appear to be thermodynamically preferred over the four-coordinate acyl monocarbonyls at low temperatures and one atmosphere of CO. Under noncatalytic (i.e., no H2 present) reaction conditions, NMR spectroscopy reveals the kinetic and thermodynamic selectivity of linear and branched acyl dicarbonyl formation. Over the range of substrates investigated, the kinetic regioselectivity observed at low temperatures under noncatalytic conditions roughly predicts the regioselectivity observed for catalytic transformations at higher temperatures and pressures. Thus, kinetic distributions of off-cycle acyl dicarbonyls constitute reasonable models for catalytic selectivity. The Wisconsin high-pressure NMR reactor (WiHP-NMRR) enables single-turnover experiments with active mixing; such experiments constitute a powerful strategy for elucidating the inherent selectivity of acyl formation and acyl hydrogenolysis in hydroformylation reactions.
authors.affiliation: Department of Chemistry, University of Wisconsin-Madison , 1101 University Avenue, Madison, Wisconsin 53706, United States.
authors.forename: Eleanor R
authors.initials: ER
authors.lastname: Nelsen
authors.affiliation: Department of Chemistry, University of Wisconsin-Madison , 1101 University Avenue, Madison, Wisconsin 53706, United States.
authors.forename: Anna C
authors.initials: AC
authors.lastname: Brezny
authors.affiliation: Department of Chemistry, University of Wisconsin-Madison , 1101 University Avenue, Madison, Wisconsin 53706, United States.
authors.forename: Clark R
authors.initials: CR
authors.lastname: Landis