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Silylenes, divalent silicon(II) compounds, once considered highly reactive and transient species, are now widely employed as stable synthons in main-group and coordination chemistry for myriad applications. The synthesis of stable silylenes represents a major breakthrough, which led to extensive exploration of silylenes in stabilizing low-valent main-group elements and as versatile ligands in coordination chemistry and catalysis. In recent years, the exploration of transition metal complexes stabilized with silylene ligands has captivated significant research attention. This is due to their robust σ-donor characteristics and capacity to stabilize transition metals in low valent states. It has also been demonstrated that the transition metal complexes of silylenes are effective catalysts for hydroboration, hydrosilylation, hydrogenation, hydrogen isotope exchange reactions, and small molecule activation chemistry. This review article focuses on the recent progress in the synthesis and catalytic application of transition metal complexes of silylenes. [ABSTRACT FROM AUTHOR]

A series of bis-metalated phosphorescent [(N^C)2Ir(bipyridine)]+ complexes with systematic variations in the structure and electronic characteristics of the N^C ligands were synthesized and characterized by using elemental analysis, mass spectrometry, NMR spectroscopy and X-ray crystallography. Investigation of the complexes' spectroscopic properties together with DFT and TD DFT calculations revealed that metal-to-ligand charge transfer (MLCT) and intraligand (LC) transition play key roles in the generation of emissive triplet states. According to the results of theoretical studies, the 3LC excited state is more accurate to consider as an intraligand charge transfer process (ILCT) between N- and C-coordinated moieties of the N^C chelate. This hypothesis is completely in line with the trends observed in the experimental absorption and emission spectra, which display systematic bathochromic shifts upon insertion of electron-withdrawing substituents into the N-coordinated fragment. An analogous shift is induced by expansion of the aromatic system of the C-coordinated fragment and insertion of polarizable sulfur atoms into the aromatic rings. These experimental and theoretical findings extend the knowledge of the nature of photophysical processes in complexes of this type and provide useful instruments for fine-tuning of their emissive characteristics. [ABSTRACT FROM AUTHOR]

This article, titled "Cover Feature: Synthesis, Reactivity, and Complexation with Fe(0) of a Tight‐bite Bis(N‐heterocyclic silylene)" explores the reactivity of a bis(N‐heterocyclic silylene) compound in two distinct reactions. The first reaction involves the formation of cyclodisilazane through the oxidative addition of N−H bonds across two SiII atoms. The second reaction with Fe(CO)5 results in the formation of a four‐membered NSi2Fe2 ring. The study provides valuable insights into the potential applications of bis(N‐heterocyclic silylene) compounds in main‐group chemistry. The full research article can be accessed for more information. [Extracted from the article]

The synthesis of the first inorganic four-membered neutral 2π-aromatic compound 2 is reported. This unique ring has been synthesized from a simple and straightforward reaction of amidinato-silylene with dichlorophenylborane, followed by the reduction with KC 8 in THF. Compound 2 has been fully characterized by single-crystal X-ray diffraction (SC-XRD), NMR spectroscopy, and mass spectrometry. The computational calculations reveal that the Si 2 B 2 ring is a π-delocalized system resulting from the interaction of p π orbital of B and Si-N σ* orbitals having pseudo π symmetry. Compound 2 is the first known example of a neutral planar inorganic analogue of cyclobutenyl dication.