title: Structure and bonding of isoleptic coinage metal (Cu, Ag, Au) dimethylaminonitrenes in the gas phase.
abstract: Dimethylaminonitrene complexes of IMesM(+) (IMes =1,3-bis(2,4,6-trimethylphenyl)imidazol-2-ylidene; M = Cu, Ag, Au) were prepared in the gas phase and structurally characterized by high-resolution infrared spectroscopy of the cold species, ion-molecule reactions, and DFT computations. We measured the binding energies of the nitrene fragment to the IMesM(+) moiety by energy-resolved collision-induced dissociation experiments in the gas phase, affording a trend in bond strength of M = Cu ≈ Au > Ag. This trend is explained in terms of a detailed metal-nitrogen bonding analysis, from which relativistic effects on the bonding were assessed. Various density functionals were evaluated for reproducing the observed thermochemical data and Truhlar's M06 functional was found to give the best agreement.
authors.affiliation: Laboratorium für Organische Chemie, ETH Zürich, Wolfgang-Pauli-Strasse 10, CH-8093 Zürich, Switzerland.
authors.forename: Alexey
authors.initials: A
authors.lastname: Fedorov
authors.forename: Erik P A
authors.initials: EP
authors.lastname: Couzijn
authors.forename: Natalia S
authors.initials: NS
authors.lastname: Nagornova
authors.forename: Oleg V
authors.initials: OV
authors.lastname: Boyarkin
authors.forename: Thomas R
authors.initials: TR
authors.lastname: Rizzo
authors.forename: Peter
authors.initials: P
authors.lastname: Chen
mesh_terms: D003300:Copper / Q000737:chemistry*; D005740:Gases / Q000737:chemistry; D006046:Gold / Q000737:chemistry*; D056004:Molecular Dynamics Simulation; D015394:Molecular Structure; D009942:Organometallic Compounds / Q000138:chemical synthesis / Q000737:chemistry*; D012834:Silver / Q000737:chemistry*
chemical_list: D005740:Gases; D009942:Organometallic Compounds; D012834:Silver; D006046:Gold; D003300:Copper