Structure and Bonding of Isoleptic Coinage Metal (Cu, Ag, Au) Dimethylaminonitrenes in the Gas Phase
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- 作者：Alexey Fedorov ; Erik P. A. Couzijn ; Natalia S. Nagornova ; Oleg V. Boyarkin ; Thomas R. Rizzo ; Peter Chen
- 刊名：Journal of the American Chemical Society
- 出版年：2010
- 出版时间：October 6, 2010
- 年：2010
- 卷：132
- 期：39
- 页码：13789-13798
- 全文大小：510K
- 年卷期：v.132,no.39(October 6, 2010)
- ISSN：1520-5126
文摘
Dimethylaminonitrene complexes of IMesMp>+ p> (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 IMesMp>+ p> 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.