On the Nature of the Bonding in Coinage Metal Halides

This article analyzes the nature of the chemical bond in coinage metal halides using high-level ab initio Valence Bond (VB) theory. It is shown that these bonds display a large Charge-Shift Bonding character, which is traced back to the large Pauli pressure arising from the interaction between the bond pair with the filled semicore d shell of the metal. The gold-halide bonds turn out to be pure Charge-Shift Bonds (CSBs), while the copper halides are polar-covalent bonds and silver halides borderline cases. Among the different halogens, the largest CSB character is found for fluorine, which experiences the largest Pauli pressure from its σ lone pair. Additionally, all these bonds display a secondary but non-negligible π bonding character, which is also quantified in the VB calculations.

Construction of Stable Metal-Organic Framework Platforms Embedding N-Heterocyclic Carbene Metal Complexes for Selective Catalysis

We report a bottom-up approach to immobilize catalysts into MOFs, including copper halides and gold chloride in a predictable manner. Interestingly, the structures of MOFs bearing NHC metal complexes maintained a similar 4-fold interpenetrated cube. They exhibited exceptionally high porosity despite the interpenetrated structure and showed good stability in various solvents. Moreover, these MOFs possess high size activity depending on the size of the substrates in various reactions, compared to homogeneous catalysis. Also, the high catalytic activity of MOFs can be preserved 4 times without significant loss of crystallinity. Incorporation of the various metal complexes into MOFs allows for the preparation of functional MOFs for practical applications.

Construction of Stable Metal-Organic Framework Platforms Embedding N-Heterocyclic Carbene Metal Complexes for Selective Catalysis

We report a bottom-up approach to immobilize catalysts into MOFs, including copper halides and gold chloride in a predictable manner. Interestingly, the structures of MOFs bearing NHC metal complexes maintained a similar 4-fold interpenetrated cube. They exhibited exceptionally high porosity despite the interpenetrated structure and showed good stability in various solvents. Moreover, these MOFs possess high size activity depending on the size of the substrates in various reactions, compared to homogeneous catalysis. Also, the high catalytic activity of MOFs can be preserved 4 times without significant loss of crystallinity. Incorporation of the various metal complexes into MOFs allows for the preparation of functional MOFs for practical applications.