Do Gold(III) Complexes Form Hydrogen Bonds? An Exploration of AuIII Dicarboranyl Chemistry

• Published in: Chemistry : a European journal Vol. 26; no. 4; pp. 939 - 947
• Main Authors: Chambrier, Isabelle, Hughes, David L., Jeans, Rebekah J., Welch, Alan J., Budzelaar, Peter H. M., Bochmann, Manfred
• Format: Journal Article
• Language: English
• Published: Weinheim Wiley Subscription Services, Inc 16-01-2020
• Subjects: carboranes; Chelation; Chemistry; Crystals; Gold; Hydrogen; Hydrogen bonding; Hydrogen bonds; Ligands; Mathematical analysis; Organic chemistry; organometallic chemistry; Platinum; Pyridines; Pyridinium; trans influence; Triflic acid; Trifluoroacetic acid
• ISSN: 0947-6539; 1521-3765
• DOI: 10.1002/chem.201904790

The reaction of 1,1′‐Li2[(2,2′‐C2B10H10)2] with the cyclometallated gold(III) complex (C^N)AuCl2 afforded the first examples of gold(III) dicarboranyl complexes. The reactivity of these complexes is subject to the trans‐influence exerted by the dicarboranyl ligand, which is substantially weaker than that of non‐carboranyl anionic C‐ligands. In line with this, displacement of coordinated pyridine by chloride is only possible under forcing conditions. While treatment of (C^N)Au{(2,2′‐C2B10H10)2} (2) with triflic acid leads to Au−C rather than Au−N bond protonolysis, aqueous HBr cleaves the Au−N bond to give the pyridinium bromo complex 7. The trans‐influence of a series of ligands including dicarboranyl and bis(dicarboranyl) was assessed by means of DFT calculations. The analysis demonstrated that it was not sufficient to rely exclusively on geometric descriptors (calculated or experimental) when attempting to rank ligands for their trans influence. Complex (C^N)Au(C2B10H11)2 containing two non‐chelating dicarboranyl ligands was prepared similar to 2. Its reaction with trifluoroacetic acid also leads to Au−N cleavage to give trans‐(Hpy^C)Au(OAcF)(C2B10H11)2 (8). In crystals of 8 the pyridinium N−H bond points towards the metal centre, while in 7 it is bent away. The possible contribution of gold(III)⋅⋅⋅H−N hydrogen bonding in these complexes was investigated by DFT calculations. The results show that, unlike the situation for platinum(II), there is no evidence for an energetically significant contribution by hydrogen bonding in the case of gold(III).
The striking case of gold: The first examples of gold(III) dicarboranyl and bis(dicarboranyl) complexes are reported, including an assessment of carboranyl trans‐influence and of H‐bonding to gold(III).