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Issue 6, 2014
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Computational and experimental comparison of diphosphane and diene ligands in the Rh-catalysed carboxylation of organoboron compounds with CO2

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Abstract

The key C–C bond forming step of the Rh-catalysed carboxylation of organoboron compounds with CO2 was investigated by density functional theory (DFT) at the IEFPCM/PBE0/DGDZVP level of theory. With a bidentate phosphane (dppp) ligand, the reaction begins with a transformation from square-planar O-(η1)-bonded to distorted-tetrahedral, η2-bonded CO2 followed by migratory insertion (barrier 12.7 kcal mol−1). The calculations showed that incorporation of electron-donating substituents within either the aryl substrate or the phosphane leads to a slight decrease of the reaction barrier, in excellent agreement with the experimental trends. With a diene ligand (cod), the migratory insertion proceeds directly from the O-(η1)-bonded CO2 (barrier 17.1 kcal mol−1) as a consequence of the diminished σ-donor ability of the diene ligand. Therefore, the diene ligand is predicted to be an inferior choice compared to the diphosphane. Testing of [(cod)Rh(OH)]2 upon completion of the computations showed no conversion.

Graphical abstract: Computational and experimental comparison of diphosphane and diene ligands in the Rh-catalysed carboxylation of organoboron compounds with CO2

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Publication details

The article was received on 13 Feb 2014, accepted on 11 Apr 2014 and first published on 16 Apr 2014


Article type: Paper
DOI: 10.1039/C4GC00243A
Green Chem., 2014,16, 3224-3229

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    Computational and experimental comparison of diphosphane and diene ligands in the Rh-catalysed carboxylation of organoboron compounds with CO2

    H. Qin, J. Han, J. Hao and E. A. B. Kantchev, Green Chem., 2014, 16, 3224
    DOI: 10.1039/C4GC00243A

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