Carbon-hydrogen and carbon-carbon bond activation of cyclopropane by a hydridotris(pyrazolyl)borate rhodium complex

Wick, D D; Northcutt, T O; Lachicotte, R J; Jones, W D

doi:10.1021/om971066e

Title: Carbon-hydrogen and carbon-carbon bond activation of cyclopropane by a hydridotris(pyrazolyl)borate rhodium complex

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Abstract

Generation of the 16-electron fragment {l_brace}[HB(3,5-dimethylpyrazolyl){sub 3}]Rh(CNCH{sub 2}CMe{sub 3}){r_brace} (Tp{prime}RhL) in the presence of cyclopropane results in C-H activation of the hydrocarbon. The cyclopropyl hydride complex rearranges in benzene solvent to the metallacyclobutane complex Tp{prime}Rh(CNCH{sub 2}CMe{sub 3})(CH{sub 2}CH{sub 2}CH{sub 2}). Thermolysis of the rhodacyclobutane complex produces an {eta}{sup 2}-propylene complex. The related complex Tp{prime}Rh(CN-2,6-xylyl)(C{sub 2}H{sub 4}) has been structurally characterized and displays {eta}{sup 3}-Tp{prime} coordination, both in the solid state and in solution. Thermolysis of the rhodacyclobutane complex in the presence of neopentyl isocyanide leads to insertion of isocyanide into both Rh-C bonds of the metallacycle. Cyclobutane undergoes C-H but not C-C bond cleavage.

Authors:

Wick, D D; Northcutt, T O; Lachicotte, R J; Jones, W D ^[1]

Univ. of Rochester, NY (United States). Dept. of Chemistry

Publication Date:: Mon Sep 28 00:00:00 EDT 1998

Sponsoring Org.:: USDOE, Washington, DC (United States)

OSTI Identifier:: 315969

DOE Contract Number:: FG02-86ER13569

Resource Type:: Journal Article

Journal Name:: Organometallics

Additional Journal Information:: Journal Volume: 17; Journal Issue: 20; Other Information: PBD: 28 Sep 1998

Country of Publication:: United States

Language:: English

Subject:: 40 CHEMISTRY; CATALYTIC CRACKING; CYCLOALKANES; RHODIUM COMPLEXES; CHEMICAL ACTIVATION; CHEMICAL BONDS; X-RAY DIFFRACTION

Citation Formats


                    Wick, D D, Northcutt, T O, Lachicotte, R J, and Jones, W D. Carbon-hydrogen and carbon-carbon bond activation of cyclopropane by a hydridotris(pyrazolyl)borate rhodium complex.  United States: N. p., 1998. 
        Web.  doi:10.1021/om971066e.

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                    Wick, D D, Northcutt, T O, Lachicotte, R J, & Jones, W D. Carbon-hydrogen and carbon-carbon bond activation of cyclopropane by a hydridotris(pyrazolyl)borate rhodium complex.  United States.  https://doi.org/10.1021/om971066e

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                    Wick, D D, Northcutt, T O, Lachicotte, R J, and Jones, W D. 1998.  
        "Carbon-hydrogen and carbon-carbon bond activation of cyclopropane by a hydridotris(pyrazolyl)borate rhodium complex".  United States.  https://doi.org/10.1021/om971066e.

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@article{osti_315969,

  title        = {Carbon-hydrogen and carbon-carbon bond activation of cyclopropane by a hydridotris(pyrazolyl)borate rhodium complex},

  author       = {Wick, D D and Northcutt, T O and Lachicotte, R J and Jones, W D},

  abstractNote = {Generation of the 16-electron fragment {l_brace}[HB(3,5-dimethylpyrazolyl){sub 3}]Rh(CNCH{sub 2}CMe{sub 3}){r_brace} (Tp{prime}RhL) in the presence of cyclopropane results in C-H activation of the hydrocarbon. The cyclopropyl hydride complex rearranges in benzene solvent to the metallacyclobutane complex Tp{prime}Rh(CNCH{sub 2}CMe{sub 3})(CH{sub 2}CH{sub 2}CH{sub 2}). Thermolysis of the rhodacyclobutane complex produces an {eta}{sup 2}-propylene complex. The related complex Tp{prime}Rh(CN-2,6-xylyl)(C{sub 2}H{sub 4}) has been structurally characterized and displays {eta}{sup 3}-Tp{prime} coordination, both in the solid state and in solution. Thermolysis of the rhodacyclobutane complex in the presence of neopentyl isocyanide leads to insertion of isocyanide into both Rh-C bonds of the metallacycle. Cyclobutane undergoes C-H but not C-C bond cleavage.},

  doi          = {10.1021/om971066e},

  url          = {https://www.osti.gov/biblio/315969},
  journal      = {Organometallics},
number       = 20,

  volume       = 17,

  place        = {United States},

  year         = {Mon Sep 28 00:00:00 EDT 1998},

  month        = {Mon Sep 28 00:00:00 EDT 1998}

}

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