title: Ligand influence on metal aggregation: a unique bonding mode for pyridylpyrrolides.
abstract: The synthesis and characterization of a Cu(I) complex with a cis-bidentate monoanionic nitrogenous ligand, 2-pyridylpyrrolide, L, is reported. This shows binding of one base B = MeCN or CO per copper in a species LCu(B), but this readily releases the volatile ligand under vacuum with aggregation of transient LCu to a mixture of two enantiomers of a chiral trimer: a zwitterion containing inequivalent Cu(I) centers, possible via a new bonding mode of pyridylpyrrolide, and one with nitrogen lone pairs donating to two different metals. Density functional theory calculations show the energetics of both ligand binding and aggregation (including dimer and monomer alternatives), as well as the ability of this ligand to rotate away from planarity to accommodate a bridging structural role. The trimer serves as a synthon for the simple fragment LCu.
authors.affiliation: Department of Chemistry and Molecular Structure Center, Indiana University, Bloomington, Indiana 47405, USA.
authors.forename: José G
authors.initials: JG
authors.lastname: Andino
authors.forename: Jaime A
authors.initials: JA
authors.lastname: Flores
authors.forename: Jonathan A
authors.initials: JA
authors.lastname: Karty
authors.forename: Joseph P
authors.initials: JP
authors.lastname: Massa
authors.forename: Hyunsoo
authors.initials: H
authors.lastname: Park
authors.forename: Nikolay P
authors.initials: NP
authors.lastname: Tsvetkov
authors.forename: Robert J
authors.initials: RJ
authors.lastname: Wolfe
authors.forename: Kenneth G
authors.initials: KG
authors.lastname: Caulton