Aryl boronic acids and esters are important building blocks in API synthesis. The palladium-catalyzed Suzuki-Miyaura borylation is the most common method for their preparation. This paper describes an improvement of the current reaction conditions. By using lipophilic bases such as potassium 2-ethyl hexanoate, the borylation reaction could be achieved at 35 °C in less than 2 h with very low palladium loading (0.5 mol %). A preliminary mechanistic study shows a hitherto unrecognized inhibitory effect by the carboxylate anion on the catalytic cycle, whereas 2-ethyl hexanoate minimizes this inhibitory effect. This improved methodology enables borylation of a wide range of substrates under mild conditions.

The thermodynamics of halogen bonding of a series of isostructural Group 10 metal pincer fluoride complexes of the type [(3,5‐R2‐tBuPOCOPtBu)MF] (3,5‐R2‐tBuPOCOPtBu=κ3‐C6HR2‐2,6‐(OPtBu2)2 with R=H, tBu, COOMe; M=Ni, Pd, Pt) and iodopentafluorobenzene was investigated. Based on NMR experiments at different temperatures, all complexes 1‐tBu (R=tBu, M=Ni), 2‐H (R=H, M=Pd), 2‐tBu (R=tBu, M=Pd), 2‐COOMe (R=COOMe, M=Pd) and 3‐tBu (R=tBu, M=Pt) form strong halogen bonds with Pd complexes showing significantly stronger binding to iodopentafluorobenzene. Structural and computational analysis of a model adduct of complex 2‐tBu with 1,4‐diiodotetrafluorobenzene as well as of structures of iodopentafluorobenzene in toluene solution shows that formation of a type I contact occurs.

The synthesis of 3,5-disubstituted cyclometalated iridium(iii) hydrido complexes of the type [3,5-R(POCOP)IrHX] (3,5-R(POCOP) = κ-CHR-2,6-(OPtBu) with R = t-Bu, COOMe; X = Cl, H) is described. All complexes were investigated in the catalytic dehydrogenation of hydrazine borane and compared with the unsubstituted compounds [(POCOP)IrHX] (X = Cl, H). All catalysts are highly active and recyclable, clearly maintaining hydrogen production activity. The dehydrogenation products were structurally characterised by solid state NMR and FTIR spectroscopy. Experimental observations were complemented by a dispersion-corrected DFT study to rationalise the mechanism of hydrazine borane dehydrogenation.

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The reaction of 1,3‐dimercaptobenzene with iPr2PCl in the presence of the base NaH, furnishes the symmetric ligand [C6H4‐1,3‐(SPiPr2)2] (1a). The direct reaction of this ligand as well as of the literature‐known nonsymmetric ligand [C6H4‐1‐(SPiPr2)‐3‐(OPiPr2)] (1b) with NiCl2 affords the symmetric bis(thiophosphinito) PSCSP pincer complex [{C6H3‐2,6‐(SPiPr2)2}NiCl] (2a) as well as the phosphinito–thiophosphinito POCSP pincer complex [{C6H3‐2‐(SPiPr2)‐6‐(OPiPr2)}NiCl] (2b). Both complexes were fully characterised and their catalytic performance in Kumada coupling of aryl halides and p‐tolylmagnesium bromide under mild conditions was evaluated.