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Stabilization of low oxidation gold anions as aurate or auride by organic ligands has long been a synthetic challenge, owing to the proneness of low-valent gold centres to cluster. Despite being the most electronegative metal, isolable gold(I) aurate complexes have only been obtained from a few σ-withdrawing organo- and organo-main group ligands. Stabilization of highly-reduced gold complexes by π-modulating redox active ligands has only been achieved by cyclic (amino)(alkyl)carbene (CAAC), which is limited to 1e

To stabilize S

In this study, we afford explicit characterizations of electronic and geometrical structures of recently reported hypervalent penta-coordinate carbon compounds by using gas-phase characterization techniques: photodissociation spectroscopy (PDS) and ion mobility-mass spectrometry (IM-MS). In particular for a compound with moderately electron donating ligand bearing p-methylthiophenyl substituents, the coexistence of tetra- and penta-coordinate isomers are confirmed, consistent with the solution characterizations. It is in sharp contrast to the exclusive tetra-coordinate form (with normal valence of the central carbon atom) in the single crystal. This suggests that non-polar environment makes penta-coordinate structure thermodynamically most stable. This delicate difference between the tetra- and penta-coordinate structures dependent on environments is a close reflection of the lower activation barrier of SN2 reaction found under neutral solvent or gas-phase reactions.

Herein, we report detailed studies on a series of