Platinum phosphinothiolato hydride complexes: synthesis, structure and evaluation as tin-free hydroformylation catalysts

Dalton Transactions : an International Journal of Inorganic Chemistry
Julio RealÁngel Álvarez-Larena

Abstract

Ligand 2-diphenylphosphinothiophenol (Hsarp) reacted with Pt(PPh3)4 to yield trans-[PtH(sarp)(PPh3)], which undergoes fast exchange with free PPh3 on the NMR time scale and very slowly and reversibly formed some cis-[PtH(sarp)(PPh3)] over time in solution (11%, 24 h). Reaction of trans-[PtH(sarp)(PPh3)] with Hsarp in boiling toluene gave cis- and trans-[Pt(sarp)2]; the cis isomer being more stable. These complexes were characterized by (1)H and (31)P NMR and also analyzed by XRD in the case of trans-[PtH(sarp)(PPh3)], trans-[Pt(sarp)2], and cis-[Pt(sarp)2]. trans-[PtH(sarp)(PPh3)] was evaluated as a preformed, tin-free hydroformylation catalyst on styrene and found active at 100 °C, at pressures over 75 bar, yielding phenylpropanal (regioselectivities up to 83% in 2-phenylpropanal), with total conversions to aldehydes up to 100% at styrene/platinum ratios from 400/1 to 1000/1 and minimal hydrogenation products.

References

Mar 5, 2004·Journal of the American Chemical Society·Anthony HaynesRob J Watt
Aug 21, 2007·Inorganic Chemistry·Craig A GrapperhausMark S Mashuta
Aug 8, 2008·Journal of the American Chemical Society·Yasuhiro OhkiKazuyuki Tatsumi
Sep 4, 2012·Chemical Reviews·Robert FrankeArmin Börner
Feb 26, 2013·Angewandte Chemie·Jola PospechMatthias Beller
Jun 17, 2016·ChemistryOpen·Josep DuranAlbert Poater

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