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Resonance Character of Copper/Silver/Gold Bonding in Small Molecule⋅⋅⋅MX (X=F, Cl, Br, CH 3 , CF 3 ) Complexes
Author(s) -
Zhang Guiqiu,
Yue Huanjing,
Weinhold Frank,
Wang Hui,
Li Hong,
Chen Dezhan
Publication year - 2015
Publication title -
chemphyschem
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.016
H-Index - 140
eISSN - 1439-7641
pISSN - 1439-4235
DOI - 10.1002/cphc.201500211
Subject(s) - chemistry , resonance (particle physics) , crystallography , intermolecular force , natural bond orbital , ligand (biochemistry) , molecule , chemical bond , copper , hyperconjugation , stereochemistry , atomic physics , physics , organic chemistry , biochemistry , receptor
The resonance character of Cu/Ag/Au bonding is investigated in B⋅⋅⋅MX (M=Cu, Ag, Au; X=F, Cl, Br, CH 3 , CF 3 ; B=CO, H 2 O, H 2 S, C 2 H 2 , C 2 H 4 ) complexes. The natural bond orbital/natural resonance theory results strongly support the general resonance‐type three‐center/four‐electron (3c/4e) picture of Cu/Ag/Au bonding, B:MX↔B + M:X − , which mainly arises from hyperconjugation interactions. On the basis of such resonance‐type bonding mechanisms, the ligand effects in the more strongly bound OC⋅⋅⋅MX series are analyzed, and distinct competition between CO and the axial ligand X is observed. This competitive bonding picture directly explains why CO in OC⋅⋅⋅AuCF 3 can be readily replaced by a number of other ligands. Additionally, conservation of the bond order indicates that the idealized relationship b B⋅⋅⋅M + b MX =1 should be suitably generalized for intermolecular bonding, especially if there is additional partial multiple bonding at one end of the 3c/4e hyperbonded triad.