Fluoroarene Complexes with Small Bite Angle Bisphosphines : Routes to Amine–Borane and Aminoborylene Complexes

Fluoroarene complexes of the small bite angle bisphosphine Cy2PCH2PCy2 (dcpm) have been prepared: [Rh(dcpm)(η6-1,2-F2C6H4)][Al{OC(CF3)3}4] and [Rh(dcpm)(η6-1,2,3-F3C6H3)][Al{OC(CF3)3}4]. These complexes act as precursors to a previously inaccessible σ-amine–borane complex [Rh(dcpm)(η2-H3B·NMe3)][Al{OC(CF3)3}4] of a small bite-angle phosphine. This complex is a poor catalyst for the dehydrocoupling of H3B·NMe2H. Instead, formation of the bridging borylene complex [{RhH(µ-dcpm)}2(µ-H)(µ-BNMe2)][Al{OC(CF3)3}4] occurs, which has been studied by NMR, mass spectrometry, crystallographic and DFT techniques. This represents a new route to bridging borylene complexes

Extrusion processing of sweet potato

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C-C cross-coupling reactions by palladium on barium and potassium polyoxotungstate supports

A heterogeneous catalyst system for Suzuki and Heck coupling reactions was developed using polyoxometalates as supports for palladium. The catalyst system was synthesized in a one step process using sodium phosphotungstate and palladium acetate. We used the supported catalyst in organic media without the need for special ligands. Substantial activity was observed after several recycles. The catalyst showed high product selectivity with yields up to > 95 % in both Suzuki and Heck reactions

Epoxidation of olefins with molecular oxygen as the oxidant using gold catalysts supported on polyoxometalates

4 We report a highly efficient green process for the epoxidation of various olefins using polyoxometalate-supported gold nanoparticles as catalysts and using oxygen as the terminal oxidant. The nanoparticles were prepared through thermal reduction of Au(III) and were characterised by TEM and XPS. The elemental composition of the catalyst was also determined using ICP. The results show that higher calcination temperatures give a higher degree of reduction, but also result in some sintering of the particles. The catalytic epoxidation reaction may be carried out with or without a solvent and with air or molecular oxygen as the stoichiometric oxidant and using t-butyl hydroperoxide as an initiator. The method shows consistently high conversions and >90% selectivity to epoxide formation for norbornene and cyclooctene oxidation. The catalysts show little deactivation with time and are easily recovered by filtration and can be reused with little or no loss in activity and selectivity