title: Synthesis and characterization of heterobimetallic complexes with direct Cu-M bonds (M = Cr, Mn, Co, Mo, Ru, W) supported by N-heterocyclic carbene ligands: a toolkit for catalytic reaction discovery.
abstract: Building upon the precedent of catalytically active (NHC)Cu-FeCp(CO)2 complexes, a series of (NHC)Cu-[M] complexes were synthesized via the addition of Na(+)[M](-) reagents to (NHC)CuCl synthons. The different [M](-) anions used span a range of 7 × 10(7) relative nucleophilicity units, allowing for controlled variation of nucleophile/electrophile pairing in the heterobimetallic species. Direct Cu-M bonds (M = Cr, Mn, Co, Mo, Ru, W) formed readily when the bulky IPr carbene was used as a support. Crystallographic characterization and computational examination of these complexes was conducted. For the smaller IMes carbene, structural isomerism was observed when using the weakest [M](-) nucleophiles, with (IMes)Cu-[M] and {(IMes)2Cu}{Cu[M]2} isomers being observed in equilibrium. Collectively, the series of complexes provides a toolbox for catalytic reaction discovery with precise control of structure-function relationships.
authors.affiliation: Department of Chemistry, University of Illinois at Chicago , 845 West Taylor Street, Chicago, Illinois 60607, United States.
authors.forename: Suparna
authors.initials: S
authors.lastname: Banerjee
authors.forename: Malkanthi K
authors.initials: MK
authors.lastname: Karunananda
authors.forename: Sharareh
authors.initials: S
authors.lastname: Bagherzadeh
authors.forename: Upul
authors.initials: U
authors.lastname: Jayarathne
authors.forename: Sean R
authors.initials: SR
authors.lastname: Parmelee
authors.forename: Greyson W
authors.initials: GW
authors.lastname: Waldhart
authors.forename: Neal P
authors.initials: NP
authors.lastname: Mankad