The Ozerov group has previously reported an Ir complex supported by a SiNN pincer ligand which is an efficient and chemoselective catalyst for dehydrogenative borylation of terminal alkynes (DHBTA). In order to elucidate the mechanism of DHBTA or improve the current catalytic system, we decided to investigate the properties of the analogous Rh system since Rh and Ir complexes often exhibit comparable reactivity as group 9 metals. The (SiNN)Rh(H)(COE) complex was successfully synthesized from [Rh(COE)2Cl]2 and the sodium salt of the SiNN ligand, and was shown to react with excess pinacolborane to form the (SiNN)Rh(H)(Bpin)2 complex. Both (SiNN)Rh(H)(COE) and (SiNN)Rh(H)(Bpin)2 complexes have been characterized and exhibit different catalytic reactivity from the analogous Ir complexes. The reactivity of these Rh complexes toward terminal alkynes and arenes is discussed. Using X-ray crystallography, interesting structural differences between the catalytically active Rh and Ir species have been observed, serving as an explanation for the reactivity difference.

Investigation into the structure of (SiNN)Rh complexes and their borylation reactivity toward terminal alkynes and arenes

247th National Meeting (2014)

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