title: Single-Molecule Investigation of Initiation Dynamics of an Organometallic Catalyst.
abstract: The action of molecular catalysts comprises multiple microscopic kinetic steps whose nature is of central importance in determining catalyst activity and selectivity. Single-molecule microscopy enables the direct examination of these steps, including elucidation of molecule-to-molecule variability. Such molecular diversity is particularly important for the behavior of molecular catalysts supported at surfaces. We present the first combined investigation of the initiation dynamics of an operational palladium cross-coupling catalyst at the bulk and single-molecule levels, including under turnover conditions. Base-initiated kinetics reveal highly heterogeneous behavior indicative of diverse catalyst population. Unexpectedly, this distribution becomes more heterogeneous at increasing base concentration. We model this behavior with a two-step saturation mechanism and identify specific microscopic steps where chemical variability must exist in order to yield observed behavior. Critically, we reveal how structural diversity at a surface translates into heterogeneity in catalyst behavior, while demonstrating how single-molecule experiments can contribute to understanding of molecular catalysts.
authors.affiliation: Department of Chemistry, The University of Wisconsin-Madison , 1101 University Avenue, Madison, Wisconsin 53706, United States.
authors.forename: James D
authors.initials: JD
authors.lastname: Ng
authors.affiliation: Department of Chemistry, The University of Wisconsin-Madison , 1101 University Avenue, Madison, Wisconsin 53706, United States.
authors.forename: Sunil P
authors.initials: SP
authors.lastname: Upadhyay
authors.affiliation: Department of Chemistry, The University of Wisconsin-Madison , 1101 University Avenue, Madison, Wisconsin 53706, United States.
authors.forename: Angela N
authors.initials: AN
authors.lastname: Marquard
authors.affiliation: Department of Chemistry, The University of Wisconsin-Madison , 1101 University Avenue, Madison, Wisconsin 53706, United States.
authors.forename: Katherine M
authors.initials: KM
authors.lastname: Lupo
authors.affiliation: Department of Chemistry, The University of Wisconsin-Madison , 1101 University Avenue, Madison, Wisconsin 53706, United States.
authors.forename: Daniel A
authors.initials: DA
authors.lastname: Hinton
authors.affiliation: Department of Chemistry, The University of Wisconsin-Madison , 1101 University Avenue, Madison, Wisconsin 53706, United States.
authors.forename: Nicolas A
authors.initials: NA
authors.lastname: Padilla
authors.affiliation: Department of Chemistry, The University of Wisconsin-Madison , 1101 University Avenue, Madison, Wisconsin 53706, United States.
authors.forename: Desiree M
authors.initials: DM
authors.lastname: Bates
authors.affiliation: Department of Chemistry, The University of Wisconsin-Madison , 1101 University Avenue, Madison, Wisconsin 53706, United States.
authors.forename: Randall H
authors.initials: RH
authors.lastname: Goldsmith