Stability and trans Influence in Fluorinated Gold(I) Coordination Compounds

We examined the Au–P and Au–X chemical bonding scenario throughout the series of compounds of the general formula [AuX(LP)] wherein LP is triphenylphosphine or a fluorinated phosphine [PPhF = P(C6H5)2(C6F5) 1, P(C6H5)(C6F5)2 2 and P(C6F5)3 3] and X is chloride or a fluorinated thiolate [SRF = SCF3 a, SCH2CF3 b, SC6F5 c, SC6F4(CF3)‐4 d]. We found that the increase of the fluorination degree or the replacement of Cl– by a –SRF ligand decreases the stability of the compound. Furthermore, this substitution shifts the 31P‐NMR signals to low field, which indicates differences in the electronegativity of the phosphorus due to the distinct trans influences of the Cl– and –SRF species. These effects correlate with the charge of the gold atom coordinated to phosphorus. Our investigation shows the high potential of fluorination as a strategy for the modulation of the properties of gold compounds, for example in catalysis, and the applicability of quantum chemical topology studies in the explanation of these features. Experimental and theoretical examination of the influence of fluorination of the ligands on the stability and electronic structure of a series of gold(I) compounds bearing fluorinated phosphines and thiolates are presented.