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Predicting Stable Molecular Structures for (RNC) 2 Au I X Complexes
Author(s) -
Rabaâ Hassan,
Chiheb Mohamed,
Balch Alan L.,
Sundholm Dage
Publication year - 2019
Publication title -
zeitschrift für anorganische und allgemeine chemie
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.354
H-Index - 66
eISSN - 1521-3749
pISSN - 0044-2313
DOI - 10.1002/zaac.201900134
Subject(s) - isocyanide , cyanide , chemistry , thiocyanate , crystallography , chalcogen , ligand (biochemistry) , halide , molecular geometry , stereochemistry , molecule , inorganic chemistry , biochemistry , receptor , organic chemistry
Calculations have been performed at the MP2 and DFT levels for investigating the reasons for the difficulties in synthesizing bis(isocyanide)gold(I) halide complexes. Three‐coordinated gold(I) complexes of the type (R 3 P) 2 Au I X ( 1 ) can be synthesized, whereas the analogous isocyanide complexes (RNC) 2 Au I X ( 2 ) are not experimentally known. The molecular structures of (R 3 P) 2 Au I X (X = Cl, Br, and I) and (RNC) 2 Au I X with X = halide, cyanide, nitrite, methylthiolate, and thiocyanate are compared and structural differences are discussed. Calculations of molecular properties elucidate which factors determine the strength of the gold‐ligand interactions in (RNC) 2 Au I X. The linear bonding mode of RNC favors a T‐shaped geometry instead of the planar Y‐shaped trigonal structure of (R 3 P) 2 Au I X complexes that have been synthesized. An increased polarity of the Au–X bond in 2 leads to destabilization of the Y‐shaped structure. Chalcogen‐containing ligands or cyanide appear to be good X‐ligand candidates for synthesis of (RNC) 2 Au I X complexes.