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Syntheses, crystal structures, reactivity, and photochemistry of gold(III) bromides bearing N-heterocyclic carbenes.

TLDR
Reactions of the Au(III) complexes towards anionic ligands like carboxylates, phenolates and thiophenolates were investigated and result in a complete or partial reduction to a Au(I) complex.
Abstract
Gold(I) complexes bearing N-heterocyclic carbenes (NHC) of the type (NHC)AuBr (3a/3b) [NHC = 1-methyl-3-benzylimidazol-2-ylidene (= MeBnIm), and 1,3-dibenzylimidazol-2-ylidene (= Bn2Im)] are prepared by transmetallation reactions of (tht)AuBr (tht = tetrahydrothiophene) and (NHC)AgBr (2a/2b). The homoleptic, ionic complexes [(NHC)2Au]Br (6a/6b) are synthesized by the reaction with free carbene. Successive oxidation of 3a/3b and 6a/6b with bromine gave the respective (NHC)AuBr3 (4a/4b) and [(NHC)2AuBr2]Br (7a/7b) in good overall yields as yellow powders. All complexes were characterized by NMR spectroscopy, mass spectrometry, elemental analysis and single crystal X-ray diffraction. Reactions of the Au(III) complexes towards anionic ligands like carboxylates, phenolates and thiophenolates were investigated and result in a complete or partial reduction to a Au(I) complex. Irradiation of the Au(III) complexes with UV light yield the Au(I) congeners in a clean photo-reaction.

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Recent Advances in Gold(III) Chemistry: Structure, Bonding, Reactivity, and Role in Homogeneous Catalysis.

TL;DR: A deeper understanding of fundamental organometallic reactivity of gold(III) has revealed unexpected mechanistic avenues, which can open when the barriers for reactions that for other metals would be regarded as "standard" are too high.
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Exploiting a dimeric silver transmetallating reagent to synthesize macrocyclic tetracarbene complexes

TL;DR: In this article, a dimeric macrocyclic tetra-N-heterocyclic carbene (NHC) complex was synthesized and shown to successfully extend transmetallation of polydentate NHCs beyond bidentate nHCs.
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References
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Balanced basis sets of split valence, triple zeta valence and quadruple zeta valence quality for H to Rn: Design and assessment of accuracy

TL;DR: A large set of more than 300 molecules representing all elements-except lanthanides-in their common oxidation states was used to assess the quality of the bases all across the periodic table, and recommendations are given which type of basis set is used best for a certain level of theory and a desired quality of results.
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Density-functional approximation for the correlation energy of the inhomogeneous electron gas

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COSMO : a new approach to dielectric screening in solvents with explicit expressions for the screening energy and its gradient

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Journal ArticleDOI

Electronic structure calculations on workstation computers: the program system turbomole

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