Insight into the mechanism of decarbonylation of methanol by ruthenium complexes; a deuterium labelling study

Patrizia Lorusso; Graham Eastham; David J. Cole-Hamilton

doi:10.1039/C8DT01733F

Insight into the mechanism of decarbonylation of methanol by ruthenium complexes; a deuterium labelling study

Patrizia Lorusso, Graham Eastham, David J. Cole-Hamilton

School of Chemistry

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

Abstract

In the reaction of [RuHClP₃] (P = PPh₃) with NaOMe in methanol, the product is [RuH₂(CO)P₃]. Short reaction times show that the final product is formed through [RuH₄P₃] as the major intermediate. Using NaOCD₃ in CD₃OD, the first formed product is [RuH₄P'₃] (P' is PPh₃ partially deuterated in the ortho positions of the aromatic rings). Further reaction leads to a mixture of [RuH_nD_2-n(CO)P₃] (n = 0, 22 %; n = 1, 2 isomers each 28 %; n = 2, 22 %). Mechanistic aspects of both steps of the reaction are explored and, together with previously published calculations, they provide definitive mechanisms for both dehydrogenation and decarbonylation in these interesting systems.

Original language	English
Journal	Dalton Transactions
Volume	In press
Early online date	15 Jun 2018
DOIs	https://doi.org/10.1039/C8DT01733F
Publication status	E-pub ahead of print - 15 Jun 2018

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10.1039/C8DT01733F

Lorusso labelling revised
© 2018 the Authors. This work has been made available online in accordance with the publisher’s policies. This is the author created accepted version manuscript following peer review and as such may differ slightly from the final published version. The final published version of this work is available at https://doi.org/10.1039/C8DT01733F
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title = "Insight into the mechanism of decarbonylation of methanol by ruthenium complexes; a deuterium labelling study",

abstract = "In the reaction of [RuHClP3] (P = PPh3) with NaOMe in methanol, the product is [RuH2(CO)P3]. Short reaction times show that the final product is formed through [RuH4P3] as the major intermediate. Using NaOCD3 in CD3OD, the first formed product is [RuH4P'3] (P' is PPh3 partially deuterated in the ortho positions of the aromatic rings). Further reaction leads to a mixture of [RuHnD2-n(CO)P3] (n = 0, 22 %; n = 1, 2 isomers each 28 %; n = 2, 22 %). Mechanistic aspects of both steps of the reaction are explored and, together with previously published calculations, they provide definitive mechanisms for both dehydrogenation and decarbonylation in these interesting systems.",

author = "Patrizia Lorusso and Graham Eastham and Cole-Hamilton, {David J.}",

note = "The authors thank Lucite international for funding. ",

year = "2018",

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day = "15",

doi = "10.1039/C8DT01733F",

language = "English",

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T1 - Insight into the mechanism of decarbonylation of methanol by ruthenium complexes; a deuterium labelling study

AU - Lorusso, Patrizia

AU - Eastham, Graham

AU - Cole-Hamilton, David J.

N1 - The authors thank Lucite international for funding.

PY - 2018/6/15

Y1 - 2018/6/15

N2 - In the reaction of [RuHClP3] (P = PPh3) with NaOMe in methanol, the product is [RuH2(CO)P3]. Short reaction times show that the final product is formed through [RuH4P3] as the major intermediate. Using NaOCD3 in CD3OD, the first formed product is [RuH4P'3] (P' is PPh3 partially deuterated in the ortho positions of the aromatic rings). Further reaction leads to a mixture of [RuHnD2-n(CO)P3] (n = 0, 22 %; n = 1, 2 isomers each 28 %; n = 2, 22 %). Mechanistic aspects of both steps of the reaction are explored and, together with previously published calculations, they provide definitive mechanisms for both dehydrogenation and decarbonylation in these interesting systems.

AB - In the reaction of [RuHClP3] (P = PPh3) with NaOMe in methanol, the product is [RuH2(CO)P3]. Short reaction times show that the final product is formed through [RuH4P3] as the major intermediate. Using NaOCD3 in CD3OD, the first formed product is [RuH4P'3] (P' is PPh3 partially deuterated in the ortho positions of the aromatic rings). Further reaction leads to a mixture of [RuHnD2-n(CO)P3] (n = 0, 22 %; n = 1, 2 isomers each 28 %; n = 2, 22 %). Mechanistic aspects of both steps of the reaction are explored and, together with previously published calculations, they provide definitive mechanisms for both dehydrogenation and decarbonylation in these interesting systems.

UR - http://www.rsc.org/suppdata/c8/dt/c8dt01733f/c8dt01733f1.pdf

U2 - 10.1039/C8DT01733F

DO - 10.1039/C8DT01733F

M3 - Article

SN - 1477-9226

VL - In press

JO - Dalton Transactions

JF - Dalton Transactions

ER -

Insight into the mechanism of decarbonylation of methanol by ruthenium complexes; a deuterium labelling study

Abstract

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