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

Julio Real, Esther Prat-Gil, Montserrat Pagès-Barenys, Alfonso Polo, Joan F. Piniella, Ángel Álvarez-Larena

Research output: Contribution to journalArticleResearchpeer-review

2 Citations (Scopus)

Abstract

© The Royal Society of Chemistry 2016. 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 1H and 31P 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.
Original languageEnglish
Pages (from-to)3964-3973
JournalDalton Transactions
Volume45
Issue number9
DOIs
Publication statusPublished - 1 Jan 2016

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