title: Dynamic, Reversible Oxidative Addition of Highly Polar Bonds to a Transition Metal.
abstract: The combination of Pt0complexes and indium trihalides leads to compounds that form equilibria in solution between their In-X oxidative addition (OA) products (PtIIindyl complexes) and their metal-only Lewis pair (MOLP) isomers (LnPt→InX3). The position of the equilibria can be altered reversibly by changing the solvent, while the equilibria can be reversibly and irreversibly driven toward the MOLP products by addition of further donor ligands. The results mark the first observation of an equilibrium between MOLP and OA isomers, as well as the most polar bond ever observed to undergo reversible oxidative addition to a metal complex. In addition, we present the first structural characterization of MOLP and oxidative addition isomers of the same compound. The relative energies of the MOLP and OA isomers were calculated by DFT methods, and the possibility of solvent-mediated isomerization is discussed.
authors.forename: Rüdiger
authors.initials: R
authors.lastname: Bertermann
authors.forename: Julian
authors.initials: J
authors.lastname: Böhnke
authors.forename: Holger
authors.initials: H
authors.lastname: Braunschweig
authors.forename: Rian D
authors.initials: RD
authors.lastname: Dewhurst
authors.forename: Thomas
authors.initials: T
authors.lastname: Kupfer
authors.forename: Jonas H
authors.initials: JH
authors.lastname: Muessig
authors.affiliation: Department of Chemistry, School of Life Sciences, University of Sussex , Brighton, Sussex BN1 9QJ, United Kingdom.
authors.forename: Leanne
authors.initials: L
authors.lastname: Pentecost
authors.forename: Krzysztof
authors.initials: K
authors.lastname: Radacki
authors.affiliation: Catalysis Division, CSIR - National Chemical Laboratory , Pashan, Pune 411008, India.
authors.forename: Sakya S
authors.initials: SS
authors.lastname: Sen
authors.affiliation: Department of Chemistry, School of Life Sciences, University of Sussex , Brighton, Sussex BN1 9QJ, United Kingdom.
authors.forename: Alfredo
authors.initials: A
authors.lastname: Vargas