A new anionic heteroleptic Ir(III)-dithiolate complex Ir(ppy)2(benzene-1,2-dithiolate) (ppy = 2-phenylpyridine, [IrSS](-)) undergoes very fast air oxidation to form a monosulfinate complex [IrSSO2](-), which can be further dioxygenated by O2 or H2O2 to give a disulfinate complex [IrSO2SO2](-), which has been characterized by X-ray crystallography. The dioxygenation is accompanied by changes in the electronic structures of the complexes, leading to blue shift of emission from [IrSS](-) (λ(max) = 665 nm) to [IrSSO2](-) (λ(max) = 556 nm) and to [IrSO2SO2](-) (λ(max) = 460 nm). The molecular and electronic structures of the complexes are probed by DFT calculations. Time-dependent DFT (TD-DFT) calculations show the lowest energy spin-allowed electronic transitions for [IrSS](-) and [IrSSO2](-) are mainly ligand (3p orbital of S)-to-ligand (π* orbitals of ppy)-charge-transfer transition, whereas the lowest energy electronic transition in [IrSO2SO2](-) is predominantly metal-to-ligand-charge transfer in nature.

The reaction of germylone (L)Ge (1) [L = 3-Ad-1-{C((t)Bu) = N(Mes)}C3H4N2] with 1 equivalent of MeOTf afforded a germyliumylidene ion [(L)GeMe](+)OTf(-) (2), while reactions with M(CO)5(thf) (M = Cr, Mo, W) gave the corresponding germylone-metal complexes [(L)Ge]M(CO)5 (3-5). The former possesses a pyramidal Ge center, whereas the latter display a planar geometry around the Ge atom. Computational studies showed a unique bonding interaction between 1 and the M(CO)5 unit, which involves a σ-donation as well as a weak π-back-donation.

The first dibenzo[a,e]disilapentalene with two SiC moieties in the heteropentalene core has been prepared. Its solid-state structure and density functional theory (DFT) calculations revealed that the SiC bonds are involved in an expanded πconjugated system. The SiC bonds show a distinguished reactivity toward CO 2 , depending on the reaction conditions. While one product results from fixation of two CO 2 molecules across one SiC bond, two different products could be isolated from the reaction of three CO 2 molecules with both SiC bonds. The mechanism has been uncovered by DFT calculations. P entalene is a classical hydrocarbon composed of two fused cyclopentadiene rings with intrinsic Huckel antiaromaticity, which dimerizes even at −100 °C. 1 Through benzannulation as in dibenzo[a,e]pentalene I (Figure 1), the antiaromatic

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An isolable 1,4,2-diazaborole derivative was synthesized and structurally characterized. X-ray diffraction analysis and computational studies revealed a delocalization of 6π-electrons over the BC2N2 five-membered ring, which thus indicates the aromatic property. The reactivity toward electrophiles such as MeOTf and selectfluor was also investigated.