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

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

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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.
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Original languageEnglish
JournalDalton Transactions
VolumeIn press
Early online date15 Jun 2018
DOIs
Publication statusE-pub ahead of print - 15 Jun 2018

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