Over the years, hydrosilylation of terminal alkenes has emerged as one most prominent applications homogeneous catalysis. While relevant reports concern β-selective hydrosilylation, yielding linear products which are industrial importance, opposite selectivity is also gaining increasing interest and sets scene for next challenges. Markovnikov alkenes, especially in its asymmetric variant, become aim development new catalytic systems successfully implementing base-metal complexes—one trends...

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

We present a reaction system based on simple nickel(II) salen-type complexes as efficient precatalysts for selective hydrosilylation of olefins with selectivity dependent the type substrates used. The system...

Highly regioselective hydrosilylation of olefins with aryl- and alkoxysilanes has been developed using a simple sodium triethylborohydride.

We present the results of our research on use microwaves as an unconventional heat source for acceleration iridium(III) chloro-bridged dimer preparation. The enabled us to revise and improve known guidelines very quick highly efficient synthesis dimeric complexes in a simple isolation manner. According developed methodology, already dimers containing ligands based 2-phenylpyridinato motif, well new ones stabilized with functionalized benzo[h]quinolinato 2-phenoxypyridinato-based ligands,...

Sodium trialkylborohydrides were found to be initiators of selective hydrogermylation aromatic alkenes. Addition phenylgermane and diphenylgermane in the presence 10 mol% NaHB(sec-Bu)3 proceeded a highly manner give - contrast analogous hydrosilylation process β-germylated products. The nature this was explained with aid DFT calculations it proposed that mechanism proceeds via trisubstituted germanide anion whose attack on terminal vinyl carbon is source selectivity.

A detailed DFT study reveals the mechanism of trialkylborohydride-catalysed Markovnikov hydrosilylation aromatic alkenes.

A series of bench-stable Co(II) complexes containing hydrazone Schiff base ligands were evaluated in terms their activity and selectivity carbon-carbon multiple bond transfer hydrogenation. These cobalt complexes, especially a precatalyst bearing pyridine-2-yl-N(Me)N=C-(1-methyl)imidazole-2-yl ligand, activated by LiHBEt3, successfully used the hydrogenation substituted styrenes phenylacetylenes with ammonia borane as hydrogen source. Key advantages reported catalytic system include mild...

Alkoxysilanes find application in many areas of chemistry ranging from research-scale organic synthesis to multi-ton production materials. Classically, they are obtained stoichiometric reaction alcoholysis chlorosilanes, however, recent years brought development the field direct dehydrogenative coupling hydrosilanes with alcohols, which is a more atom-economic and benign alternative former process. In this paper, we report use sodium tri(sec-butyl)borohydride as convenient promoter reaction....

Sodium triethylborohydride, a popular hydride transferring reagent, is commonly used as an activating agent for hydroboration catalysts based on the first-row transition metal complexes. It has been found that NaHBEt3 can be selective catalyst of terminal alkynes with pinacolborane. Hydroboration aromatic and aliphatic in presence 10 mol% proceeded highly manner to give (E)-vinylboronate esters high yields, whereas ethynylsilanes seem less reactive this process. Internal also transformed...

Molybdenum-based catalysts are among the best candidates to achieve alkyne metathesis. They can be either well-defined carbynes, previously synthesized before their use, but also prepared in situ upon using stable molybdenum carbonyl complexes, or high oxidation state salts that need a previous alkylation, both type of precursors being "activated" by hydroxyl-containing compounds such as phenols and silanols. This paper is presenting studies made on these systems, directed towards knowledge...

( E )‐β‐Iodoenamides and )‐β‐iodoenimides can be easily obtained from N ‐vinyl derivatives ‐vinylamides ‐vinylimides) by stereoselective ruthenium‐catalysed silylative coupling with vinyltrimethylsilane (Marciniec coupling) subsequent stereospecific silicon–iodine exchange. Bromodesilylation of )‐β‐silylenimides affords )‐β‐bromoenimides, while the analogous reactions involving )‐β‐silylenamides lead to decomposition substrates. ‐Halosuccinimides have been found as most effective...

A systematic study on the use of silanols and phenols as effective activators in Mo(CO)₆ – based catalytic systems for metathesis 4-decyne 1-phenyl-1-propyne is reported. In comparison with traditionally used phenols, aryl-substituted exhibit high activating potential molybdenum species even at lower concentrations (2 mol% 4–20 silanol depending alkyne) toluene reflux. Silylated are also suitable co-catalysts. Additionally, Mo(CO)₆/silanol system shown to be efficiently activated by...

C,N-cyclopalladated complexes are among the most robust and widely used (pre)catalysts of cross-coupling reactions, combining long shelf life with high catalytic activity. In this report, we describe synthesis properties new Pd(II) a flexidentate ligand – 2,2-dimethyl-5-(2-pyridyl)pentane-3,5-dione (HL). Its coordinating resulted in formation two stereoisomeric cis- trans-PdL2 each one O,O- other N,C(sp3)-coordination modes. The solid-state structures have been established by means...

Alkyne metathesis in multicomponent catalytic systems, although subject to changes, is still dominated by molybdenum hexacarbonyl as a source of Mo(0). Our findings show that this coordination compound relatively inert under conditions, which results noticeably long induction activity, and the kinetics transformation can greatly benefit from switching more labile Mo(0) complexes. Several easily obtainable ones were tested [Mo(CO)3(py)3] has been chosen one exhibiting most desired features,...

Abstract (E)‐β‐Iodoenamides and (E)‐β‐iodoenimides can be easily obtained from N‐vinyl derivatives (N‐vinylamides N‐vinylimides) by stereoselective ruthenium‐catalyzed silylative coupling with vinyltrimethylsilane (Marciniec coupling) subsequent stereospecific silicon—iodine exchange.