Structure–Reactivity Studies, Characterization, and Transformation of Intermediates by Lithium Chloride in the Direct Insertion of Alkyl and Aryl Iodides to Metallic Zinc Powder

Feng, Chao; Easter, Quinn T.; Blum, Suzanne A.

doi:10.1021/acs.organomet.6b00910

Title: Structure–Reactivity Studies, Characterization, and Transformation of Intermediates by Lithium Chloride in the Direct Insertion of Alkyl and Aryl Iodides to Metallic Zinc Powder

Abstract

Employment of fluorophore-tagged alkyl and aryl iodides permitted detection of persistent surface intermediates during their direct insertion to commercially available zinc powder. The sensitivity of this subensemble microscopy technique enabled structure–reactivity studies in the formation of intermediates that are present in quantities sufficiently low as to have been undetected previously by traditional ensemble analytical techniques. In these surface intermediates we transformed them using lithium chloride, which lead to the assignment of the mechanistic role of lithium chloride as changing the rate-determining step in the reaction by lowering the barrier for solubilization of these otherwise persistent surface organometallic intermediates. The temperature dependence/qualitative barrier of the direct insertion step was determined independently from the solubilization step and from the barrier for the overall reaction. Detection of these zinc surface intermediates at the single-molecule level, i.e., of individual surface organometallic species, has been achieved for the first time. Energy dispersive X-ray spectroscopy (EDS) measurements of the elemental composition of the surface of the zinc powder determined that lithium chloride does not clean the surface of the oxides; instead, pretreatment of the surface with TMSCl effects partial removal of surface oxides after the 2 h pretreatment time previously reported in the empirically optimized syntheticmore »« less

Authors:

Feng, Chao ^[1]; Easter, Quinn T. ^[1];

^[1]

Department of Chemistry, University of California, Irvine, California 92697-2025, United States

Publication Date:: Fri Feb 03 00:00:00 EST 2017

Research Org.:: Univ. of California, Irvine, CA (United States)

Sponsoring Org.:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

OSTI Identifier:: 1342413

Alternate Identifier(s):: OSTI ID: 1372302

Grant/Contract Number:: FG02-08ER15994; CHE-1464959; CHE-082913

Resource Type:: Published Article

Journal Name:: Organometallics

Additional Journal Information:: Journal Name: Organometallics Journal Volume: 36 Journal Issue: 13; Journal ID: ISSN 0276-7333

Publisher:: American Chemical Society

Country of Publication:: United States

Language:: English

Subject:: 36 MATERIALS SCIENCE; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats


                    Feng, Chao, Easter, Quinn T., and Blum, Suzanne A. Structure–Reactivity Studies, Characterization, and Transformation of Intermediates by Lithium Chloride in the Direct Insertion of Alkyl and Aryl Iodides to Metallic Zinc Powder.  United States: N. p., 2017. 
Web.  doi:10.1021/acs.organomet.6b00910.

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                    Feng, Chao, Easter, Quinn T., & Blum, Suzanne A. Structure–Reactivity Studies, Characterization, and Transformation of Intermediates by Lithium Chloride in the Direct Insertion of Alkyl and Aryl Iodides to Metallic Zinc Powder.  United States.  https://doi.org/10.1021/acs.organomet.6b00910

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                    Feng, Chao, Easter, Quinn T., and Blum, Suzanne A. Fri .  
"Structure–Reactivity Studies, Characterization, and Transformation of Intermediates by Lithium Chloride in the Direct Insertion of Alkyl and Aryl Iodides to Metallic Zinc Powder".  United States.  https://doi.org/10.1021/acs.organomet.6b00910.

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@article{osti_1342413,

  title        = {Structure–Reactivity Studies, Characterization, and Transformation of Intermediates by Lithium Chloride in the Direct Insertion of Alkyl and Aryl Iodides to Metallic Zinc Powder},

  author       = {Feng, Chao and Easter, Quinn T. and Blum, Suzanne A.},

  abstractNote = {Employment of fluorophore-tagged alkyl and aryl iodides permitted detection of persistent surface intermediates during their direct insertion to commercially available zinc powder. The sensitivity of this subensemble microscopy technique enabled structure–reactivity studies in the formation of intermediates that are present in quantities sufficiently low as to have been undetected previously by traditional ensemble analytical techniques. In these surface intermediates we transformed them using lithium chloride, which lead to the assignment of the mechanistic role of lithium chloride as changing the rate-determining step in the reaction by lowering the barrier for solubilization of these otherwise persistent surface organometallic intermediates. The temperature dependence/qualitative barrier of the direct insertion step was determined independently from the solubilization step and from the barrier for the overall reaction. Detection of these zinc surface intermediates at the single-molecule level, i.e., of individual surface organometallic species, has been achieved for the first time. Energy dispersive X-ray spectroscopy (EDS) measurements of the elemental composition of the surface of the zinc powder determined that lithium chloride does not clean the surface of the oxides; instead, pretreatment of the surface with TMSCl effects partial removal of surface oxides after the 2 h pretreatment time previously reported in the empirically optimized synthetic procedure. The current limitations of this microscopy approach are also determined and discussed with respect to the addition of solid reagents during in operando imaging. Characterization of the resulting soluble fluorophore-tagged organozinc/LiCl complex by 1H NMR spectroscopy, mass spectrometry, and fluorescence spectroscopy provided insight into its solution dynamics and chemical exchange processes.},

  doi          = {10.1021/acs.organomet.6b00910},

  journal      = {Organometallics},

  number       = 13,

  volume       = 36,

  place        = {United States},

  year         = {Fri Feb 03 00:00:00 EST 2017},

  month        = {Fri Feb 03 00:00:00 EST 2017}

}

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Catalyst‐Free Reductive Coupling of Aromatic and Aliphatic Nitro Compounds with Organohalides
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Catalyst‐Free Reductive Coupling of Aromatic and Aliphatic Nitro Compounds with Organohalides
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Rauser, Marian; Eckert, Raphael; Gerbershagen, Max
Angewandte Chemie International Edition, Vol. 58, Issue 20
DOI: 10.1002/anie.201814197

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