Over the years, hydrosilylation of terminal alkenes has emerged as one of the most prominent applications of homogeneous catalysis. While most of the relevant reports concern β-selective hydrosilylation, yielding linear products which are of industrial importance, the opposite selectivity is also gaining increasing interest and sets the scene for the next challenges. Markovnikov hydrosilylation of alkenes, especially in its asymmetric variant, has become the aim of development of new catalytic systems successfully implementing base-metal complexesone of the most prominent trends in contemporary catalysis. In this Perspective, we present the current state of this topic and the way it has been achieved, with special emphasis put on the issues still unresolved and prospective directions of development based on the trends present in the literature, but without unnecessary attention to some details of only historical significance.

The first example of sodium triethylborohydride-catalysed hydrosilylation of alkenes is reported. The hydrosilylation of certain alkenes, in particular styrenes, vinylsilanes and allyl glycidyl ether, with aromatic hydrosilanes proceeded in a highly regioselective manner to give Markovnikov products. It is significant that several protocols use NaHBEt as a reducing agent generating active catalysts in situ of other hydrosilylation reactions. An anionic mechanism of hydrosilylation is proposed.

Recent advances in ruthenium-catalysed hydrosilylation of C–C multiple bonds and its application to organic synthesis are highlighted.

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We present the results of our research on the use of microwaves as an unconventional heat source for the acceleration of iridium­(III) chloro-bridged dimer preparation. The results enabled us to revise and improve known guidelines for the very quick and highly efficient synthesis of iridium­(III) dimeric complexes in a very simple isolation manner. According to the developed methodology, the already known dimers containing ligands based on the 2-phenylpyridinato motif, as well as new ones stabilized with functionalized benzo­[h]­quinolinato and 2-phenoxypyridinato-based ligands, were efficiently synthesized. The scope of the incorporated ligands included compounds equipped with electron-donating (−Me, −OMe, −OPh, −NMe2), electron-withdrawing (−F, −Br, −CF3, −C6F5), and hole-transporting (−NPh2, −C6H4NPh2) groups. The obtained complexes were characterized by NMR, X-ray diffraction, and electrospray ionization mass spectrometry methods, and their behavior was examined in the presence of coordinating solvents such as dimethyl sulfoxide and acetonitrile. Investigation of the interactions between the above-mentioned solvents and dimers enabled us to confirm the ability of the former to cleave μ-chloride bridges, which enriches the knowledge in the field of organometallic chemistry. This knowledge can be particularly useful for the scientists working in the field of iridium-based materials, helping to avoid misinterpretation of the spectroscopic data.