title: Assessment of the electronic structure of 2,2'-pyridylpyrrolides as ligands.
abstract: The ligand class 2,2'-pyridylpyrrolide is surveyed, both for its structural features and its electronic structure, when attached to monovalent K, Cu, Ag, Au, and Rh. The influence of pyrrolide ring substituents is studied, as well as the question of push/pull interaction between the pyridyl and pyrrolide halves. The π donor ability of the pyrrolide is found to be less than that of an analogous phenyl. However, in contrast to the phenyl analog, the HOMO is pyrrolide π in character for pyridylpyrrolide complexes of copper and rhodium, while it is conventionally metal localized for planar, d(8) rhodium pyridylphenyl. Monovalent three-coordinate copper complexes show great deviations from Y-shaped toward T-shaped structures, including cases where the pyridyl ligand bonds only weakly.
authors.affiliation: Department of Chemistry, Indiana University, Bloomington, Indiana 47405, USA.
authors.forename: Jaime A
authors.initials: JA
authors.lastname: Flores
authors.forename: José G
authors.initials: JG
authors.lastname: Andino
authors.forename: Nikolay P
authors.initials: NP
authors.lastname: Tsvetkov
authors.forename: Maren
authors.initials: M
authors.lastname: Pink
authors.forename: Robert J
authors.initials: RJ
authors.lastname: Wolfe
authors.forename: Ashley R
authors.initials: AR
authors.lastname: Head
authors.forename: Dennis L
authors.initials: DL
authors.lastname: Lichtenberger
authors.forename: Joseph
authors.initials: J
authors.lastname: Massa
authors.forename: Kenneth G
authors.initials: KG
authors.lastname: Caulton
mesh_terms: D004583:Electrons; D008024:Ligands; D008958:Models, Molecular; D015394:Molecular Structure; D009942:Organometallic Compounds / Q000138:chemical synthesis / Q000737:chemistry*; D010084:Oxidation-Reduction; D011758:Pyrroles / Q000138:chemical synthesis / Q000737:chemistry*; D011789:Quantum Theory
chemical_list: D008024:Ligands; D009942:Organometallic Compounds; D011758:Pyrroles