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

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

This work was financially supported by the Dirección General de Enseñanza Superior e Investigación Científica (DGESIC) of Spain though project BQU2002-04070-C02

© Dalton Transactions, 2016, vol. 45, p. 3964-3973

Royal Society of Chemistry (RSC)

Author: Real i Obradors, Juli
Prat-Gil, Esther
Pagès-Barenys, Montserrat
Polo Ortiz, Alfonso
Piniella, Joan F.
Álvarez-Larena, Ángel
Date: 2016
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 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
This work was financially supported by the Dirección General de Enseñanza Superior e Investigación Científica (DGESIC) of Spain though project BQU2002-04070-C02
Format: application/pdf
ISSN: 1477-9226 (versió paper)
1477-9234 (versió electrònica)
Document access: http://hdl.handle.net/10256/12348
Language: spa
Publisher: Royal Society of Chemistry (RSC)
Collection: MICYT/PN 2002-2005/BQU2002-04070-C02-01
Reproducció digital del document publicat a: http://dx.doi.org/10.1039/c5dt04107d
Articles publicats (D-Q)
Is part of: © Dalton Transactions, 2016, vol. 45, p. 3964-3973
Rights: Tots els drets reservats
Subject: Metalls de transició -- Compostos
Transition metal compounds
Reaccions químiques
Chemical reactions
Funcional de densitat, Teoria del
Density functionals
Title: Platinum phosphinothiolato hydride complexes: Synthesis, structure and evaluation as tin-free hydroformylation catalysts
Type: info:eu-repo/semantics/article
Repository: DUGiDocs

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