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Facile O-atom insertion into C-C and C-H bonds by a trinuclear copper complex designed to harness a singlet oxene

Chen, Peter P.-Y. and Yang, Richard B.-G. and Lee, Jason C.-M. and Chan, Sunney I. (2007) Facile O-atom insertion into C-C and C-H bonds by a trinuclear copper complex designed to harness a singlet oxene. Proceedings of the National Academy of Sciences of the United States of America, 104 (37). pp. 14570-14575. ISSN 0027-8424. PMCID PMC1976241. https://resolver.caltech.edu/CaltechAUTHORS:CHEpnas07b

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[img] PDF (Supporting Information Figure 7. ESI mass spectrum of the oxygenated [CuICuICuI(7-Et)]1+(BF4-), together with their simulated mass spectra.) - Supplemental Material
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[img] PDF (Supporting Information Figure 8. ESI mass spectrum of the oxygenated [CuICuICuI(7-Me)]1+(ClO4-).) - Supplemental Material
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[img] PDF (Supporting Information Figure 9. Nanospray-ESI mass spectrum of the benzoic adduct {[CuIICuIICuII(7-Et)(O)]2+(ClO4-) + PhCOOH}+.) - Supplemental Material
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[img] PDF (Supporting Information Figure 10. Nanospray-ESI mass spectrum of the benzoic adduct {[CuIICuIICuII(7-Et)(O)]2+(BF4-) + PhCOOH}+.) - Supplemental Material
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[img] PDF (Supporting Information Figure 11. Nanospray-ESI mass spectrum {[CuIICuIICuII(7-Et)(O)]2+(ClO4-)2 + H}+ and the acetic acid adduct {[CuIICuIICuII(7-Et)(O)]2+(ClO4-) + CH3COOH}+.) - Supplemental Material
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[img] PDF (Supporting Information Figure 12. Comparisons of the nanospray-ESI mass spectra obtained by reoxidation of [CuICuICuI(7-Et)]1+(ClO4-) complexes with 16O2 (a) and 18O2 (b).) - Supplemental Material
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[img] PDF (Supporting Information Figure 13. Nanospray-ESI mass spectrum of benzoic acid adduct {[CuIICuIICuII(7-Et)(O)]2+(BF4-) + PhCOOH}+ together with the acetic acid adduct {[CuII4uIICuII(7-Et)(O)]2+(BF4-) + CH3COOH}+.) - Supplemental Material
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[img] PDF (Supporting Information Figure 14. Representation of the x-ray crystal structure of {[CuIICuIICuII(7-Et)(O)](BF4-)2}2(PF6-).) - Supplemental Material
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Abstract

Two trinuclear copper [CuICuICuI(L)]1+ complexes have been prepared with the multidentate ligands (L) 3,3'-(1,4-diazepane-1,4-diyl)bis(1-((2-(dimethylamino)ethyl)(methyl)amino)propan-2-ol) (7-Me) and (3,3'-(1,4-diazepane-1,4-diyl)bis(1-((2-(diethylamino) ethyl)(ethyl) amino)propan-2-ol) (7-Et) as models for the active site of the particulate methane monooxygenase (pMMO). The ligands were designed to form the proper spatial and electronic geometry to harness a "singlet oxene," according to the mechanism previously suggested by our laboratory. Consistent with the design strategy, both [CuICuICuI(L)]1+ reacted with dioxygen to form a putative bis(µ3-oxo)CuIICuIICuIII species, capable of facile O-atom insertion across the central C-C bond of benzil and 2,3-butanedione at ambient temperature and pressure. These complexes also catalyze facile O-atom transfer to the C-H bond of CH3CN to form glycolonitrile. These results, together with our recent biochemical studies on pMMO, provide support for our hypothesis that the hydroxylation site of pMMO contains a trinuclear copper cluster that mediates C-H bond activation by a singlet oxene mechanism.


Item Type:Article
Related URLs:
URLURL TypeDescription
https://www.ncbi.nlm.nih.gov/pmc/articles/PMC1976241/PubMed CentralArticle
https://doi.org/10.1073/pnas.0707119104DOIUNSPECIFIED
https://doi.org/10.1073/pnas.0707119104DOIUNSPECIFIED
ORCID:
AuthorORCID
Chan, Sunney I.0000-0002-5348-2723
Additional Information:© 2007 by The National Academy of Sciences of the USA. Communicated by Harry B. Gray, California Institute of Technology, Pasadena, CA, July 31, 2007 (received for review March 30, 2007). Published online on September 5, 2007, 10.1073/pnas.0707119104. We thank Dr. Mei-Chun Tseng of the Institute of Chemistry of Academia Sinica for kind assistance in nanospray ESI-MS, Yi-Hung Liu of the Instrumentation Center of National Taiwan University in Taipei for solving the x-ray structure, and Dr. Michael K. Chan of the Department of Biochemistry and Chemistry at Ohio State University (Columbus, OH) for numerous discussions on this scientific project as well as valuable comments on this manuscript. This work was supported by Academia Sinica and by grants from the National Science Council (NSC95-2113-M-001-046-MY2) in Taiwan. Author contributions: P.P.-Y.C., R.B.-G.Y., and J.C.-M.L. performed research; S.I.C. designed research; S.I.C. contributed new reagents/analytic tools; P.P.-Y.C. and S.I.C. analyzed data; and P.P.-Y.C. and S.I.C. wrote the paper. The authors declare no conflict of interest. This article contains supporting information online at www.pnas.org/cgi/content/full/0707119104/DC1.
Funders:
Funding AgencyGrant Number
Academia SinicaUNSPECIFIED
National Science Council (Taipei)NSC 95-2113-M-001-046-MY2
Subject Keywords:density functional theory; methane monooxygenase; membrane-bound or particulate methane monooxygenase; soluble methane monooxygenase; mass spectroscopy
Issue or Number:37
PubMed Central ID:PMC1976241
Record Number:CaltechAUTHORS:CHEpnas07b
Persistent URL:https://resolver.caltech.edu/CaltechAUTHORS:CHEpnas07b
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:9901
Collection:CaltechAUTHORS
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Deposited On:26 Mar 2008
Last Modified:03 Oct 2019 00:04

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