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Synthesis of osmium and ruthenium complexes bearing dimethyl (S,S)-2,2′-(pyridine-2,6-diyl)-bis-(4,5-dihydrooxazol-4-carboxylate) ligand and application to catalytic H/D exchange

Young, Kenneth J. H. and Lokare, Kapil S. and Leung, Chin Hin and Cheng, Mu-Jeng and Nielsen, Robert J. and Petasis, Nicos A. and Goddard, William A., III and Periana, Roy A. (2011) Synthesis of osmium and ruthenium complexes bearing dimethyl (S,S)-2,2′-(pyridine-2,6-diyl)-bis-(4,5-dihydrooxazol-4-carboxylate) ligand and application to catalytic H/D exchange. Journal of Molecular Catalysis A: Chemical, 339 (1-2). pp. 17-23. ISSN 1381-1169. https://resolver.caltech.edu/CaltechAUTHORS:20110601-092305453

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Abstract

Using tridentate, neutral PyBox ligands, several new osmium and ruthenium complexes [M(PyBox)Cl_(2)(C_(2)H_(4)), where M = Ru, Os] have been prepared, all thermally stable. Some of these PyBox compounds are active for C–H activation of benzene. The Os(PyBox)Cl_(2)(C_(2)H_(4) complex was characterized by X-ray diffraction. DFT calculations (B3LYP and M06 including Poisson–Boltzmann solvation) corroborate that the Os/PyBox complex in acetic acid (ΔG‡ = 32.0 kcal/mol) is more reactive for benzene C–H activation than Ru/PyBox in basic conditions (ΔG‡ = 34.8 kcal/mol at pH = 13). The stability of hydroxide- and chloride-bridged dinuclear resting states determines calculated barriers.


Item Type:Article
Related URLs:
URLURL TypeDescription
http://dx.doi.org/10.1016/j.molcata.2011.01.029DOIArticle
http://www.sciencedirect.com/science/article/pii/S1381116911000434PublisherArticle
ORCID:
AuthorORCID
Cheng, Mu-Jeng0000-0002-8121-0485
Nielsen, Robert J.0000-0002-7962-0186
Goddard, William A., III0000-0003-0097-5716
Periana, Roy A.0000-0001-7838-257X
Additional Information:© 2011 Elsevier B.V. Received 24 November 2010; revised 25 January 2011; accepted 27 January 2011. Available online 9 February 2011. The authors thank the Chevron Energy Technology Company, the Center for Catalytic Hydrocarbon Functionalization, Energy Frontier Research Center (DOE DE-SC000-1298), Scripps Florida and National Science Foundation (CHE-0328121) for financial support.
Funders:
Funding AgencyGrant Number
Chevron Energy Technology CompanyUNSPECIFIED
Department of Energy (DOE)DE-SC000-1298
Scripps FloridaUNSPECIFIED
NSFCHE-0328121
Subject Keywords:PyBox; C–H activation; Osmium; Ruthenium
Issue or Number:1-2
Record Number:CaltechAUTHORS:20110601-092305453
Persistent URL:https://resolver.caltech.edu/CaltechAUTHORS:20110601-092305453
Official Citation:Kenneth J.H. Young, Kapil S. Lokare, Chin Hin Leung, Mu-Jeng Cheng, Robert J. Nielsen, Nicos A. Petasis, William A. Goddard III, Roy A. Periana, Synthesis of osmium and ruthenium complexes bearing dimethyl (S,S)-2,2'-(pyridine-2,6-diyl)-bis-(4,5-dihydrooxazol-4-carboxylate) ligand and application to catalytic H/D exchange, Journal of Molecular Catalysis A: Chemical, Volume 339, Issues 1-2, 1 April 2011, Pages 17-23, ISSN 1381-1169, DOI: 10.1016/j.molcata.2011.01.029.
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:23857
Collection:CaltechAUTHORS
Deposited By: Jason Perez
Deposited On:01 Jun 2011 20:04
Last Modified:03 Oct 2019 02:50

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