title: [(B3O3H3)(n)M]+ (n = 1, 2;M = Cu, Ag, Au): a new class of metal-cation complexes.
abstract: A density functional theory (DFT) investigation into the structures and bonding characteristics of [(B3O3H3)nM](+)(n = 1, 2;M = Cu, Ag, Au) complexes was performed. DFT calculations and natural bond orbital (NBO) analyses indicate that the ΙB metal complexes of boroxine exhibit intriguing bonding characteristics, different from the typical cation-π interactions between ΙB metal-cations and benzene. The complexes of [B3O3H3M](+) and [(B3O3H3)2 M](+) (M = Cu, Ag, and Au) favor the conformation of perfectly planar structures with the C2v and D2h symmetry along one of the threefold molecular axes of boroxine, respectively. Detailed natural resonance theory (NRT) and canonical molecular orbitals (CMOs) analyses show that interaction between the metal cation and the boroxine in [B3O3H3M](+) (M = Cu, Ag, and Au) is mainly ionic, while the ΙB metal-cations←π donation effect is responsible for the binding site. In these complexes, boroxine serves as terminals η(1)-B3O3H3 with one O atom of the B3O3 ring. The infra-red (IR) spectra of [B3O3H3M](+) were simulated to facilitate their future experimental characterization. The complexes all give two IR active modes at about 1,300 and 2,700 cm(-1), which are inactive in pure boroxine. Simultaneously, the B-H stretching modes of the complexes are red-shifted due to the interaction between the metal-cation and boroxine. To explore the possibility of the structural pattern developed in this work forming mesoporous materials, complexes [(B3O3H3M)6](6+) (M = Cu, Ag, and Au) were also studied, which appear to be unique and particular interesting: they are all true minima with D6h symmetries and pore sizes ranging from 12.04 Å to 13.65 Å.
authors: Binzhou Key Laboratory of Material Chemistry, Department of Chemistry and Chemical Engineering, Binzhou University, Binzhou 256603, People's Republic of China. ldz005@126.com
authors: Da-Zhi
authors: DZ
authors: Li
authors: Chen-Chu
authors: CC
authors: Dong
authors: Shi-Guo
authors: SG
authors: Zhang
mesh_terms: D001896:Boron Compounds / Q000737:chemistry*; D056831:Coordination Complexes / Q000737:chemistry*; D003300:Copper / Q000737:chemistry*; D006046:Gold / Q000737:chemistry*; D008956:Models, Chemical; D011789:Quantum Theory; D012834:Silver / Q000737:chemistry*; D013055:Spectrophotometry, Infrared
chemical_list: D001896:Boron Compounds; D056831:Coordination Complexes; D012834:Silver; D006046:Gold; D003300:Copper
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