NDLI: Transient Ru-methyl formate intermediates generated with bifunctional transfer hydrogenation catalysts

Content Provider	PubMed Central
Author	Perry, Richard H. Brownell, Kristen R. Konstantin, Chingin Cahill, Thomas J. Waymouth, Robert M. Zare, Richard N.
Abstract	Desorption electrospray ionization (DESI) coupled to high-resolution Orbitrap mass spectrometry (MS) was used to study the reactivity of a (β-amino alcohol)(arene)RuCl transfer hydrogenation catalytic precursor in methanol (CH3OH). By placing [(p-cymene)RuCl2]2 on a surface and spraying a solution of β-amino alcohol in methanol, two unique transient intermediates having lifetimes in the submillisecond to millisecond range were detected. These intermediates were identified as Ru (II) and Ru (IV) complexes incorporating methyl formate (HCOOCH3). The Ru (IV) intermediate is not observed when the DESI spray solution is sparged with Ar gas, indicating that O2 dissolved in the solvent is necessary for oxidizing Ru (II) to Ru (IV). These proposed intermediates are supported by high-resolution and high mass accuracy measurements and by comparing experimental to calculated isotope profiles. Additionally, analyzing the bulk reaction mixture using gas chromatography-MS and nuclear magnetic resonance spectroscopy confirms the formation of HCOOCH3. These results represent an example that species generated from the (β-amino alcohol)(arene)RuCl (II) catalytic precursor can selectively oxidize CH3OH to HCOOCH3. This observation leads us to propose a pathway that can compete with the hydrogen transfer catalytic cycle. Although bifunctional hydrogen transfer with Ru catalysts has been well-studied, the ability of DESI to intercept intermediates formed in the first few milliseconds of a chemical reaction allowed identification of previously unrecognized intermediates and reaction pathways in this catalytic system.
Related Links	http://dx.doi.org/10.1073/pnas.1118934109
Starting Page	2246
File Format	PDF
ISSN	10916490
e-ISSN	10916490
Journal	Proceedings of the National Academy of Sciences of the United States of America
Issue Number	7
Volume Number	109
Language	English
Publisher	National Academy of Sciences
Publisher Date	2012-02-14
Access Restriction	Open
Rights Holder	National Academy of Sciences
Subject Keyword	Research in Higher Education
Content Type	Text
Resource Type	Article
Subject	Multidisciplinary

Sl.	Authority	Responsibilities	Communication Details
1	Ministry of Education (GoI), Department of Higher Education	Sanctioning Authority	https://www.education.gov.in/ict-initiatives
2	Indian Institute of Technology Kharagpur	Host Institute of the Project: The host institute of the project is responsible for providing infrastructure support and hosting the project	https://www.iitkgp.ac.in
3	National Digital Library of India Office, Indian Institute of Technology Kharagpur	The administrative and infrastructural headquarters of the project	Dr. B. Sutradhar bsutra@ndl.gov.in
4	Project PI / Joint PI	Principal Investigator and Joint Principal Investigators of the project	Dr. B. Sutradhar bsutra@ndl.gov.in Prof. Saswat Chakrabarti will be added soon
5	Website/Portal (Helpdesk)	Queries regarding NDLI and its services	support@ndl.gov.in
6	Contents and Copyright Issues	Queries related to content curation and copyright issues	content@ndl.gov.in
7	National Digital Library of India Club (NDLI Club)	Queries related to NDLI Club formation, support, user awareness program, seminar/symposium, collaboration, social media, promotion, and outreach	clubsupport@ndl.gov.in
8	Digital Preservation Centre (DPC)	Assistance with digitizing and archiving copyright-free printed books	dpc@ndl.gov.in
9	IDR Setup or Support	Queries related to establishment and support of Institutional Digital Repository (IDR) and IDR workshops	idr@ndl.gov.in

Transient Ru-methyl formate intermediates generated with bifunctional transfer hydrogenation catalysts

Preparation and characterization oF Ru-Sn/Al2O3 catalysts for the hydrogenation of fatty acid methyl esters

Iridium(triNHC)-Catalyzed Transfer Hydrogenation of Glycerol Carbonate without Exogenous Reductants

Ru-Sn-B/Al2O3 Catalysts for Selective Hydrogenation of Methyl Oleate: Influence of the Ru/Sn Ratio

Ru-Sn-B/TiO 2 catalysts for methyl oleate selective hydrogenation. Influence of the preparation method and the chlorine content

Conversion of 5-Methyl-3-Heptanone to C8 Alkenes and Alkane over Bifunctional Catalysts

Recent advances on bifunctional catalysts for one-pot conversion of furfural to γ-valerolactone

Fractionation of Birch Wood by Integrating Alkaline-Acid Treatments and Hydrogenation in Ethanol over a Bifunctional Ruthenium Catalyst

Support Screening Studies on the Hydrogenation of Levulinic Acid to γ-Valerolactone in Water Using Ru Catalysts

Transient Ru-methyl formate intermediates generated with bifunctional transfer hydrogenation catalysts

Similar Documents

Transient Ru-methyl formate intermediates generated with bifunctional transfer hydrogenation catalysts

Preparation and characterization oF Ru-Sn/Al2O3 catalysts for the hydrogenation of fatty acid methyl esters

Iridium(triNHC)-Catalyzed Transfer Hydrogenation of Glycerol Carbonate without Exogenous Reductants

Ru-Sn-B/Al2O3 Catalysts for Selective Hydrogenation of Methyl Oleate: Influence of the Ru/Sn Ratio

Ru-Sn-B/TiO 2 catalysts for methyl oleate selective hydrogenation. Influence of the preparation method and the chlorine content

Conversion of 5-Methyl-3-Heptanone to C8 Alkenes and Alkane over Bifunctional Catalysts

Recent advances on bifunctional catalysts for one-pot conversion of furfural to γ-valerolactone

Fractionation of Birch Wood by Integrating Alkaline-Acid Treatments and Hydrogenation in Ethanol over a Bifunctional Ruthenium Catalyst

Support Screening Studies on the Hydrogenation of Levulinic Acid to γ-Valerolactone in Water Using Ru Catalysts

Transient Ru-methyl formate intermediates generated with bifunctional transfer hydrogenation catalysts