Insight into the mechanism of decarbonylation of methanol by ruthenium complexes; a deuterium labelling study12. Issue 28 (28th June 2018)

• Record Type: Journal Article
• Authors: Lorusso, Patrizia; Eastham, Graham R.; Cole-Hamilton, David J.
• Is Part Of: Dalton transactions. Volume 47:Issue 28(2018)
• Page Start: 9411
• Page End: 9417
• Publication Date: 2018-06-28
• Subjects: Chemistry, Inorganic -- Periodicals; Chemistry, Physical and theoretical -- Periodicals; Chemistry, Inorganic -- Periodicals; 546.05
• DOI: 10.1039/c8dt01733f
• Languages: English
• ISSNs: 1477-9226

Abstract

Abstract : In the reaction of [RuHClP3 ] (P = PPh3 ) with NaOMe in methanol, the product is [RuH2 (CO)P3 ] with RuH4 P4 . 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 [RuH4 P3 ] as the major intermediate. Using NaOCD3 in CD3 OD, the first formed product is [RuH4 P′3 ] (P′ is PPh3 partially deuterated in the ortho positions of the aromatic rings). Further reaction leads to a mixture of [RuH n D2− 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.