Using Parahydrogen Induced Polarization to Study Steps in the Hydroformylation Reaction.

Simon Duckett; Dexin Guan; Cyril Godard; Stacey Polas; Robert Tooze; Adrian C. Whitwood

doi:10.1039/C8DT04723E

Using Parahydrogen Induced Polarization to Study Steps in the Hydroformylation Reaction.

Simon Duckett, Dexin Guan, Cyril Godard, Stacey Polas, Robert Tooze, Adrian C. Whitwood

Chemistry

Research output: Contribution to journal › Article › peer-review

Abstract

A range of iridium complexes, Ir(η3-C3H5)(CO)(PR2R’)2 (1a-1e) [where 1a, PR2R’ = PPh3, 1b P(p-tol)3, 1c PMePh2, 1d PMe2Ph and 1e PMe3] were synthesized and their reactivity as stoichiometric hydroformylation precursors studied. Para-hydrogen assisted NMR spectroscopy detected the following intermediates: Ir(H)2(η3-C3H5)(CO)(PR2R’) (2a-e), Ir(H)2(η1-C3H5)(CO)(PR2R’)2 (4d-e), Ir(H)2(η1-C3H5)(CO)2(PR2R’) (10a-e), Ir(H)2(CO-C3H5)(CO)2(PR2R’) (11a-c), Ir(H)2(CO-C3H7)(CO)2(PR2R’) (12a-c) and Ir(H)2(CO-C3H5)(CO)(PR2R’)2 (13d-e). Some of these species exist as two geometric isomers according to their multinuclear NMR characteristics. The NMR studies suggest a role for the following 16 electron species in these reactions: Ir(η3-C3H5)(CO)(PR2R’), Ir(η1-C3H5)(CO)(PR2R’)2, Ir(η1-C3H5)(CO)2(PR2R’), Ir(CO-C3H5)(CO)2(PR2R’), Ir(CO-C3H7)(CO)2(PR2R’) and Ir(CO-C3H5)(CO)(PR2R’)2. Their role is linked to several 18 electron species in order to confirm the route by which hydroformylation and hydrogenation proceeds.

Original language	English
Article number	C8DT04723E
Number of pages	14
Journal	Dalton Transactions
Early online date	25 Jan 2019
DOIs	https://doi.org/10.1039/C8DT04723E
Publication status	E-pub ahead of print - 25 Jan 2019

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© The Royal Society of Chemistry 2019. This is an author-produced version of the published paper. Uploaded in accordance with the publisher’s self-archiving policy. Further copying may not be permitted; contact the publisher for details.

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Cite this

@article{72f6250c27ff43759beaaf31a7d41a09,

title = "Using Parahydrogen Induced Polarization to Study Steps in the Hydroformylation Reaction.",

abstract = "A range of iridium complexes, Ir(η3-C3H5)(CO)(PR2R{\textquoteright})2 (1a-1e) [where 1a, PR2R{\textquoteright} = PPh3, 1b P(p-tol)3, 1c PMePh2, 1d PMe2Ph and 1e PMe3] were synthesized and their reactivity as stoichiometric hydroformylation precursors studied. Para-hydrogen assisted NMR spectroscopy detected the following intermediates: Ir(H)2(η3-C3H5)(CO)(PR2R{\textquoteright}) (2a-e), Ir(H)2(η1-C3H5)(CO)(PR2R{\textquoteright})2 (4d-e), Ir(H)2(η1-C3H5)(CO)2(PR2R{\textquoteright}) (10a-e), Ir(H)2(CO-C3H5)(CO)2(PR2R{\textquoteright}) (11a-c), Ir(H)2(CO-C3H7)(CO)2(PR2R{\textquoteright}) (12a-c) and Ir(H)2(CO-C3H5)(CO)(PR2R{\textquoteright})2 (13d-e). Some of these species exist as two geometric isomers according to their multinuclear NMR characteristics. The NMR studies suggest a role for the following 16 electron species in these reactions: Ir(η3-C3H5)(CO)(PR2R{\textquoteright}), Ir(η1-C3H5)(CO)(PR2R{\textquoteright})2, Ir(η1-C3H5)(CO)2(PR2R{\textquoteright}), Ir(CO-C3H5)(CO)2(PR2R{\textquoteright}), Ir(CO-C3H7)(CO)2(PR2R{\textquoteright}) and Ir(CO-C3H5)(CO)(PR2R{\textquoteright})2. Their role is linked to several 18 electron species in order to confirm the route by which hydroformylation and hydrogenation proceeds.",

author = "Simon Duckett and Dexin Guan and Cyril Godard and Stacey Polas and Robert Tooze and Whitwood, {Adrian C.}",

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T1 - Using Parahydrogen Induced Polarization to Study Steps in the Hydroformylation Reaction.

AU - Duckett, Simon

AU - Guan, Dexin

AU - Godard, Cyril

AU - Polas, Stacey

AU - Tooze, Robert

AU - Whitwood, Adrian C.

N1 - © The Royal Society of Chemistry 2019. This is an author-produced version of the published paper. Uploaded in accordance with the publisher’s self-archiving policy. Further copying may not be permitted; contact the publisher for details.

PY - 2019/1/25

Y1 - 2019/1/25

N2 - A range of iridium complexes, Ir(η3-C3H5)(CO)(PR2R’)2 (1a-1e) [where 1a, PR2R’ = PPh3, 1b P(p-tol)3, 1c PMePh2, 1d PMe2Ph and 1e PMe3] were synthesized and their reactivity as stoichiometric hydroformylation precursors studied. Para-hydrogen assisted NMR spectroscopy detected the following intermediates: Ir(H)2(η3-C3H5)(CO)(PR2R’) (2a-e), Ir(H)2(η1-C3H5)(CO)(PR2R’)2 (4d-e), Ir(H)2(η1-C3H5)(CO)2(PR2R’) (10a-e), Ir(H)2(CO-C3H5)(CO)2(PR2R’) (11a-c), Ir(H)2(CO-C3H7)(CO)2(PR2R’) (12a-c) and Ir(H)2(CO-C3H5)(CO)(PR2R’)2 (13d-e). Some of these species exist as two geometric isomers according to their multinuclear NMR characteristics. The NMR studies suggest a role for the following 16 electron species in these reactions: Ir(η3-C3H5)(CO)(PR2R’), Ir(η1-C3H5)(CO)(PR2R’)2, Ir(η1-C3H5)(CO)2(PR2R’), Ir(CO-C3H5)(CO)2(PR2R’), Ir(CO-C3H7)(CO)2(PR2R’) and Ir(CO-C3H5)(CO)(PR2R’)2. Their role is linked to several 18 electron species in order to confirm the route by which hydroformylation and hydrogenation proceeds.

AB - A range of iridium complexes, Ir(η3-C3H5)(CO)(PR2R’)2 (1a-1e) [where 1a, PR2R’ = PPh3, 1b P(p-tol)3, 1c PMePh2, 1d PMe2Ph and 1e PMe3] were synthesized and their reactivity as stoichiometric hydroformylation precursors studied. Para-hydrogen assisted NMR spectroscopy detected the following intermediates: Ir(H)2(η3-C3H5)(CO)(PR2R’) (2a-e), Ir(H)2(η1-C3H5)(CO)(PR2R’)2 (4d-e), Ir(H)2(η1-C3H5)(CO)2(PR2R’) (10a-e), Ir(H)2(CO-C3H5)(CO)2(PR2R’) (11a-c), Ir(H)2(CO-C3H7)(CO)2(PR2R’) (12a-c) and Ir(H)2(CO-C3H5)(CO)(PR2R’)2 (13d-e). Some of these species exist as two geometric isomers according to their multinuclear NMR characteristics. The NMR studies suggest a role for the following 16 electron species in these reactions: Ir(η3-C3H5)(CO)(PR2R’), Ir(η1-C3H5)(CO)(PR2R’)2, Ir(η1-C3H5)(CO)2(PR2R’), Ir(CO-C3H5)(CO)2(PR2R’), Ir(CO-C3H7)(CO)2(PR2R’) and Ir(CO-C3H5)(CO)(PR2R’)2. Their role is linked to several 18 electron species in order to confirm the route by which hydroformylation and hydrogenation proceeds.

U2 - 10.1039/C8DT04723E

DO - 10.1039/C8DT04723E

M3 - Article

SN - 1477-9234

JO - Dalton Transactions

JF - Dalton Transactions

M1 - C8DT04723E

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