Tetraphosphines with tetra(biphenyl)silane and -stannane cores as rigid scaffold linkers for immobilized catalysts

Abstract

The silane Si(p-C6H4-p-C6H4Br)4 and the stannane Sn(p-C6H4-p-C6H4Br)4 have been synthesized and characterized. For the silane a single crystal X-ray structure has been obtained. Tetralithiation of the silane with nBuLi and quenching with the corresponding chlorophosphines gave the tetraphosphines Si(p-C6H4-p-C6H4PR2)4 with (R = Ph, Cy, iPr, tBu). Tetralithiation of Sn(p-C6H4-p-C6H4Br)4 led to cleavage of the Sn-C bonds. Therefore, Sn(p-C6H4-p-C6H4PPh2)4 was synthesized by Br/Li exchange of p-Br-C6H4-p-C6H4PPh2 with nBuLi and reaction with SnCl4. The silanes have been immobilized on silica by generating three phosphonium groups per molecule that were bound to the surface via strong electrostatic interactions. The remaining phosphine group was subsequently coordinated to Wilkinson's catalyst via ligand exchange. All solids have been characterized by quantitative 31P solid-state NMR spectroscopy. The catalysts, immobilized via the tetraphosphine linker scaffolds with biphenyl spacers, showed high activities and selectivities with respect to the hydrogenation of 1-dodecene. They have been recycled 9 times in a batchwise manner. All immobilized catalysts eventually formed rhodium nanoparticles that retained their catalytic activity even after being exposed to air.