The classical radical-based hydrosilylation reaction of organic compounds bearing C−C multiple bonds is usually carried out in organic solvents and is herein presented in water with both organic solvent-soluble and water-soluble substrates. Different initiation methods to accomplish the radical-induced hydrosilylation reaction of C−C multiple bonds in water with (Me3Si)3SiH are presented. In the thermal decomposition of azo compounds, the system comprising substrate, silane, and azo-initiator (ACCN) mixed in aqueous medium at 100 °C worked well for both hydrophilic and hydrophobic substrates, with the only variation that the amphiphilic thiol HOCH2CH2SH was also needed in the case of the water-soluble compounds. Dioxygen initiation is shown to afford excellent yields of hydrosilylated products derived from substrates bearing C−C triple bonds and moderate to low yields of hydrosilylated products derived from C−C double-bonded compounds in water. Photochemical initiation in the absence of a chemical radical precursor other than the silane is also found to be a very efficient and convenient method to induce the hydrosilylation reaction of both C−C double and triple bonds of organic compounds (hydrophilic and hydrophobic substrates) with (Me3Si)3SiH in water. These three alternative radical-based methodologies studied in water are confronted.

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Glycol monoesters were produced by oxidation of acetals with oxygen, hydroperoxides, hydrogen peroxide, hydrotrioxide and ozon. Addition of salts of metals of variable valency and crown‐ether substantially increase the rate of oxidation and hydroxylation. The most efficient oxidizer is ozon.

Reaction of the palladium(II) and platinum(II) isocyanide complexes cis-[MCl 2 (CNR) 2 ] [M = Pd, R = C 6 H 3 (2,6-Me 2 ) (Xyl), 2-Cl-6-MeC 6 H 3 , cyclohexyl (Cy), t-Bu, C(Me) 2 CH 2 (Me) 3 (1,1,3,3-tetramethylbuth-1-yl abbreviated as tmbu); M = Pt, R = Xyl, 2-Cl-6-MeC 6 H 3 , Cy, t-Bu, and tmbu] with N,N′-diphenylguanidine (DPG) leads to DPG-derived metal-bound deprotonated acyclic diaminocarbene (ADC) species. This reaction occurs via a two-step process, involving the initial coupling of the guanidine with one of the isocyanides and leading to deprotonated monocarbene monochelated species, while the next addition grants the deprotonated bis-carbene bis-chelated metal compounds. DPG behaves as nucleophile, deprotonating base, and chelator. The addition of DPG proceeded with different regioselectivity depending on the metal center and, in a larger extent, on the substituent R in RNCs. The X-ray diffraction studies for the deprotonated mono-and bis-carbene complexes confirmed the regioisomerism of these species and allowed the identification of ADC protolytic forms stabilized in the solid-state. 1D ( 1 H and 13 C{ 1 H}) and 2D ( 1 H, 1 H-NOESY; 1 H, 15 N-HSQC; 1 H, 15 N-HMBC) solution NMR of the obtained systems demonstrated their configuration isomerism accompanied by prototropic tautomerism. Together, the solid-state and solution data provide an insight into the flexible character of ADC species.