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

doi:10.1039/c5dt04107d

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 journal › Article › Research › peer-review

4 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 language	English
Pages (from-to)	3964-3973
Journal	Dalton Transactions
Volume	45
Issue number	9
DOIs	https://doi.org/10.1039/c5dt04107d
Publication status	Published - 1 Jan 2016

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10.1039/c5dt04107d

CCDC 1431427: Experimental Crystal Structure Determination
Real, J. (Creator), Prat-Gil, E. (Creator), Pagès-Barenys, M. (Creator), Polo, A. (Creator), Piniella, J. F. (Creator) & Álvarez-Larena, Á. (Creator), Cambridge Crystallographic Data Centre, 23 Dec 2015
DOI: 10.5517/cc1k1j26, http://www.ccdc.cam.ac.uk/services/structure_request?id=doi:10.5517/cc1k1j26&sid=DataCite
Dataset
CCDC 1431425: Experimental Crystal Structure Determination
Real, J. (Creator), Prat-Gil, E. (Creator), Pagès-Barenys, M. (Creator), Polo, A. (Creator), Piniella, J. F. (Creator) & Álvarez-Larena, Á. (Creator), Cambridge Crystallographic Data Centre, 13 Jan 2016
DOI: 10.5517/cc1k1j04, http://www.ccdc.cam.ac.uk/services/structure_request?id=doi:10.5517/cc1k1j04&sid=DataCite
Dataset
CCDC 1431426: Experimental Crystal Structure Determination
Real, J. (Creator), Prat-Gil, E. (Creator), Pagès-Barenys, M. (Creator), Polo, A. (Creator), Piniella, J. F. (Creator) & Álvarez-Larena, Á. (Creator), Cambridge Crystallographic Data Centre, 23 Dec 2015
DOI: 10.5517/cc1k1j15, http://www.ccdc.cam.ac.uk/services/structure_request?id=doi:10.5517/cc1k1j15&sid=DataCite
Dataset

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@article{762c645ccbb743578eb2dacd77cddd1f,

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

abstract = "{\textcopyright} 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.",

author = "Julio Real and Esther Prat-Gil and Montserrat Pag{\`e}s-Barenys and Alfonso Polo and Piniella, {Joan F.} and {\'A}ngel {\'A}lvarez-Larena",

year = "2016",

month = jan,

day = "1",

doi = "10.1039/c5dt04107d",

language = "English",

volume = "45",

pages = "3964--3973",

number = "9",

}

TY - JOUR

T1 - Platinum phosphinothiolato hydride complexes: Synthesis, structure and evaluation as tin-free hydroformylation catalysts

AU - Real, Julio

AU - Prat-Gil, Esther

AU - Pagès-Barenys, Montserrat

AU - Polo, Alfonso

AU - Piniella, Joan F.

AU - Álvarez-Larena, Ángel

PY - 2016/1/1

Y1 - 2016/1/1

N2 - © 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.

AB - © 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.

U2 - 10.1039/c5dt04107d

DO - 10.1039/c5dt04107d

M3 - Article

SN - 1477-9226

VL - 45

SP - 3964

EP - 3973

JO - Dalton Transactions

JF - Dalton Transactions

IS - 9

ER -

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

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Datasets

CCDC 1431427: Experimental Crystal Structure Determination

CCDC 1431425: Experimental Crystal Structure Determination

CCDC 1431426: Experimental Crystal Structure Determination

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