Complexes of Gilman reagents with C-S and C-N double bonds: sigma or pi bonding? Academic Article

abstract

• Upon rapid injection, a variety of thiocarbonyl compounds react with the Gilman reagent Me(2)CuLi at -100 degrees C inside the probe of an NMR spectrometer to give high yields of complexes. Typical examples of substrates include carbon disulfide, methyl dithioacetate, methyl dithiobenzoate, thiobenzophenone, ethylene trithiocarbonate, and phenyl isothiocyanate. Evidence suggesting the formal oxidation state of copper in these complexes to be Cu(III) is presented. The last example was particularly interesting, since it involved a transient intermediate that was identified as a complex with a C-N double bond. Methyl isothiocyanate gave a stable C-N double-bond complex.

authors

• Thomas, Andy

published proceedings

• J Am Chem Soc

author list (cited authors)

• Bertz, S. H., Moazami, Y., Murphy, M. D., Ogle, C. A., Richter, J. D., & Thomas, A. A

citation count

• 15

complete list of authors

• Bertz, Steven H||Moazami, Yasamin||Murphy, Michael D||Ogle, Craig A||Richter, Joshua D||Thomas, Andy A

publication date

• July 2010

publisher

• American Chemical Society (ACS)  Publisher

published in

• Journal of the American Chemical Society  Journal

PubMed Central ID

• 20540520

Digital Object Identifier (DOI)

• 10.1021/ja103068h

start page

• 9549

end page

• 9551

volume

• 132

issue

• 28

URL

• http://dx.doi.org/10.1021/ja103068h