title: Substantial Dissociation Energies for the Recently Synthesized NC-Ag-NH3 and Br-Ag-NH3 Molecules and Their Isovalent Family Members M(CN)XY3 and M(Br)XY3 (M = Cu, Ag, Au; X = N, P; Y = H, F).
abstract: Chippindale et al. have recently synthesized the unique molecules (NC)Ag(NH3) and BrAg(NH3) and shown the heavy atom skeletal structures to be linear. Here, a theoretical study is reported of 12 members each of the two isovalent series of molecules. For (NC)Ag(NH3) and BrAg(NH3), the theoretical structures agree well with those determined by X-ray crystallography. Structures for the 22 yet unknown compounds should be similarly reliable. The dissociation energies for a loss of NH3 from the two known compounds are significant (34 and 31 kcal/mol), confirming their viability. For the other systems, the ligand dissociation energies are highly variable, ranging from 9 kcal/mol (BrAg-NF3) to 44 kcal/mol (BrAu-PH3). The bond dissociation energies for the different metals follow the irregular order Au > Cu > Ag. For the XY3 ligands, the dissociation energies follow the order NH3 > PH3 > PF3 > NF3, except for the BrAu-XY3 complexes. Electronic structure insights are gained via Natural Bond Orbital (NBO) analyses.
authors.affiliation: State Key Laboratory of Explosion Science and Technology, Beijing Institute of Technology, Beijing, 100081, P. R. China.|Center for Computational Quantum Chemistry, South China Normal University, Guangzhou, 510631 China.|Department of Chemistry and Center for Computational Quantum Chemistry, University of Georgia, Athens, Georgia 30602, United States.
authors.forename: Qiong
authors.initials: Q
authors.lastname: Luo
authors.affiliation: State Key Laboratory of Explosion Science and Technology, Beijing Institute of Technology, Beijing, 100081, P. R. China.|Center for Computational Quantum Chemistry, South China Normal University, Guangzhou, 510631 China.|Department of Chemistry and Center for Computational Quantum Chemistry, University of Georgia, Athens, Georgia 30602, United States.
authors.forename: Qianshu
authors.initials: Q
authors.lastname: Li
authors.affiliation: State Key Laboratory of Explosion Science and Technology, Beijing Institute of Technology, Beijing, 100081, P. R. China.|Center for Computational Quantum Chemistry, South China Normal University, Guangzhou, 510631 China.|Department of Chemistry and Center for Computational Quantum Chemistry, University of Georgia, Athens, Georgia 30602, United States.
authors.forename: Yaoming
authors.initials: Y
authors.lastname: Xie
authors.affiliation: State Key Laboratory of Explosion Science and Technology, Beijing Institute of Technology, Beijing, 100081, P. R. China.|Center for Computational Quantum Chemistry, South China Normal University, Guangzhou, 510631 China.|Department of Chemistry and Center for Computational Quantum Chemistry, University of Georgia, Athens, Georgia 30602, United States.
authors.forename: R Bruce
authors.initials: RB
authors.lastname: King
authors.affiliation: State Key Laboratory of Explosion Science and Technology, Beijing Institute of Technology, Beijing, 100081, P. R. China.|Center for Computational Quantum Chemistry, South China Normal University, Guangzhou, 510631 China.|Department of Chemistry and Center for Computational Quantum Chemistry, University of Georgia, Athens, Georgia 30602, United States.
authors.forename: Henry F
authors.initials: HF
authors.lastname: Schaefer