Rhodium boron containing

Laska, U., Frost, C.G., Plucinski, P.K. and Price, G.J. (2008) Rhodium containing magnetic nanoparticles effective catalysts for hydrogenation and the 1 4-addition of boronic acids. Catalysis Letters, 122 (1-2), 68-75. 

The rhodium-catalyzed borylation of alkanes is applied to regiospecific functionalization of polyolefines.165,165a The reaction of polypropylenes (atactic, isotactic, and syndiotactic) with B2pin2 in the presence of Cp Rh( 74-C6Me6) catalyst at 200 °G affords the borylated polymers, which are treated with basic hydrogen peroxide in a mixture of THF and H20 to oxidize the boronate esters to the corresponding alcohols (Scheme 20). The hydroxylated polymers contain 0.2-1.5% hydroxymethyl side-chains. 

Recently, a rhodium-catalyzed tandem cyclization has been reported with an arylboronic ester bearing a pendant Michael-type acceptor olefin and acetylenic65 or olefinic66 derivatives. This transformation proceeds in a water-containing medium as solvent and proton source. This catalyst system is optimized with electron-rich and bulky ligands to stabilize the rhodium intermediate and decrease the protonolysis of boron derivatives in a protic solvent. 

In the search for a reactive functional group which could be substituted on the acetylacetonate ring, chloromethylation of these chelates was attempted. The initially formed products were too reactive to be characterized directly. Treatment of rhodium acetylacetonate with chloromethyl methyl ether in the presence of boron trifluoride etherate afforded a solution of a very reactive species, apparently the chloromethyl chelate (XXX) (26). Hydrolytic workup of this intermediate yielded a polymeric mixture of rhodium chelates, but these did not contain chlorine On the basis of evidence discussed later on electrophilic cleavage of carbon from metal chelate rings and on the basis of their NMR spectra, these polymers may be of the type shown below. Reaction of the intermediate with dry ethanol afforded an impure chelate which is apparently the trisethyl ether (XXXI). Treatment of the reactive intermediate with other nucleophiles gave intractable mixtures. 

The reaction of pinacolborane with styrenes 127 in the presence of bis(chloro-l,5-cyclooctadienylrhodium) at room temperature provides styrenyl pinacol boronate 128 <1999TL2585, 2002BCJ825>. While hydroboration of alkenes is the predominant reaction with phosphine-containing rhodium catalysts such as Wilkinson s catalyst and Rh(PPh3)2COCl, dehydrogenative borylation dominates over hydroboration in the presence of phosphine-free... 

The asymmetric 1,4-addition of aryl boronic acids to a,P-unsaturated ketones has been reported with rhodium catalysts that contained P-Phos (120a) (Scheme 12.46).154... 

Treatment of aqueous solutions of bis(ethylenediamine)dichloro-rhodium(III) with sodium borohydride give solutions which the proton magnetic resonance spectrum shows to contain an Rh—H complex (t 31 p.p.m., J Rh—h 31 c.p.s.). Also, the infrared spectrum of the precipitated tetraphenyl boronate shows a band at 2100 cm-1 assigned to an Rh—H stretch. 

The insertions of olefins into metal-silyl complexes is an important step in the hydrosi-lylation of olefins, and the insertions of olefins and alkynes into metal-boron bonds is likely to be part of the mechanism of the diborations and sUaborations of substrates containing C-C multiple bonds. Other reactions, such as the dehydrogenative sUylation of olefins can also involve this step. Several studies imply that the rhodium-catalyzed hydrosilylations of olefins occur by insertion of olefins into rhodium-silicon bonds, while side products from palladium- and platinum-catalyzed hydrosilylations are thought to form by insertion of olefins into the metal-sihcon bonds. In particular, vinylsilanes are thought to form by a sequence involving olefin insertion into the metal-silicon bond, followed by p-hydrogen elimination (Chapter 10) to form the metal-hydride and vinylsilane products. 

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