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Intermolecular Aurophilic versus Intramolecular Au⋅⋅⋅N Secondary Interactions in Two‐Coordinate Gold(I) Selenolate Complexes
Author(s) -
Kole Goutam Kumar,
Wadawale Amey P.,
Nigam Sandeep,
Majumder Chiranjib,
Jain Vimal K.
Publication year - 2016
Publication title -
chemistryselect
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.437
H-Index - 34
ISSN - 2365-6549
DOI - 10.1002/slct.201601122
Subject(s) - intramolecular force , intermolecular force , chemistry , substituent , moiety , crystallography , stereochemistry , molecule , atom (system on chip) , ligand (biochemistry) , ring (chemistry) , biochemistry , receptor , organic chemistry , computer science , embedded system
A series of gold(I) selenolates viz ., [Au(Sepy‐2)(PPh 3 )] ( 1 ), [Au(Sepy‐4)(PPh 3 )] ( 2 ) (py=pyridyl), [Au(Sepyz‐2)(PPh 3 )] ( 3 ) (pyz=pyrazinyl), [Au(Sepym‐2)(PPh 3 )] ( 4 ) (pym=pyrimidyl) and [Au{Sepym(Me 2 ‐4,6)‐2}(PPh 3 )] ( 5 ) {pym‐2‐(Me 2 ‐4,6)=4,6‐dimethyl‐2‐pyrimidyl} have been synthesized and structurally characterized. The gold atom acquires a two‐coordinate linear geometry with Au−Se distance of ∼ 2.41 Å. The existence of aurophilic interactions are determined by the nature of substituent on selenium. It was observed that the complexes derived from selenolate ligand with pyridyl moiety (one hetero‐N atom in the ring) could exhibit aurophilicity; whereas, the complexes derived from ligands containing pyrazinyl and pyrimidyl moieties (two hetero‐N atoms) are devoid of such interaction but show secondary Au⋅⋅⋅N interaction. The complex [Au(Sepy‐4)(PPh 3 )] shows polymorphism and the two polymorphs differ in the relative orientations of linear molecules. There are competing secondary intramolecular Au⋅⋅⋅N interaction which plays crucial role on intermolecular aurophilic interaction and overall structure. Theoretical calculations at DFT and MP2 levels have been carried out to rationalize the experimental findings.