In this article, we report unique reactivities of hydrogensulfide (SH), disulfide (S₂), and oxydisulfide ligands (S₂O_n: n = 1-4) bridging between the Rh—Rh/Ir—Ir bonds. The hydrogensulfide and the disulfide ligand give rise to the S—C and C—C bond formation and the multi C—Cl bond activation, respectively. The oxydisulfide ligand (S₂O₄) shows a photoisomerization resulting in an intriguing crystalline-state photochromism. These reactivities are attributed mainly to the electron-rich Rh—Rh/Ir—Ir bond and the geometrical arrangement and the electronic character of the sulfide ligands.

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Synthesis, bonding, and reactivity of terminal gallylene and gallium-bridged complexes with two-coordinate gallium centers are discussed in this review. The M-Ga bonds in these complexes are dominated by the electrostatic interaction between the lone pair electrons on the Ga atom and the metal, however, covalent σ and π bonding interactions are also important for the bonding.

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Recent advance of bioinspired coordination chemistry of molybdenum and tungsten ions has been reviewed. New synthetic methods to modeling uncommon core structures, sulfido and oxo-sulfido metal centers, involved in molybdenum and tungsten enzyme active sites have been discussed. Reactivity in proton-coupled electron transfer of the model compounds also is included.

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A “molecular Borromean rings” was obtained by 2:2 condensation of difunctionalized bipyridine and diformylpyridine in the presence of M(OAc)₂ (M = Zn, Cu) in high yield. A similar template-directed reaction in the presence of equimolar amounts of Zn and Cu ions forms a “molecular Solomon’s knot”.

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Spontaneous formation of submicron sized coordination polymer particles through self-assembly of metal ions and ligands has been reported by several research groups in the last few years. In this article, preparation of those particles and their characteristic features such as fluorescent, redox, and catalytic properties were described.

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