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Yuan J, Hughes RP, Rheingold AL. A (pentafluoroethyl)(trifluoromethyl)carbene complex of iridium and reductive activation of its sp(3)α, β, and γ carbon-fluorine bonds to give perfluoro-2-butyne, perfluoro-1,2,3-butatriene and perfluoro-1-irida-2-methyl-2-cyclobutene) complexes. Dalton Trans. 2015;44(45):19518-27doi: 10.1039/c5dt02075a.
Yuan, J., Hughes, R. P., & Rheingold, A. L. (2015). A (pentafluoroethyl)(trifluoromethyl)carbene complex of iridium and reductive activation of its sp(3)α, β, and γ carbon-fluorine bonds to give perfluoro-2-butyne, perfluoro-1,2,3-butatriene and perfluoro-1-irida-2-methyl-2-cyclobutene) complexes. Dalton transactions (Cambridge, England : 2003), 44(45), 19518-27. https://doi.org/10.1039/c5dt02075a
Yuan, Jian, et al. "A (pentafluoroethyl)(trifluoromethyl)carbene complex of iridium and reductive activation of its sp(3)α, β, and γ carbon-fluorine bonds to give perfluoro-2-butyne, perfluoro-1,2,3-butatriene and perfluoro-1-irida-2-methyl-2-cyclobutene) complexes." Dalton transactions (Cambridge, England : 2003) vol. 44,45 (2015): 19518-27. doi: https://doi.org/10.1039/c5dt02075a
Yuan J, Hughes RP, Rheingold AL. A (pentafluoroethyl)(trifluoromethyl)carbene complex of iridium and reductive activation of its sp(3)α, β, and γ carbon-fluorine bonds to give perfluoro-2-butyne, perfluoro-1,2,3-butatriene and perfluoro-1-irida-2-methyl-2-cyclobutene) complexes. Dalton Trans. 2015 Dec 07;44(45):19518-27. doi: 10.1039/c5dt02075a. Epub 2015 Jul 09. PMID: 26158776.
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Dalton Trans. 2015 Dec 07;44(45):19518-27. doi: 10.1039/c5dt02075a. Epub 2015 Jul 09.

A (pentafluoroethyl)(trifluoromethyl)carbene complex of iridium and reductive activation of its sp(3)α, β, and γ carbon-fluorine bonds to give perfluoro-2-butyne, perfluoro-1,2,3-butatriene and perfluoro-1-irida-2-methyl-2-cyclobutene) complexes.

Dalton transactions (Cambridge, England : 2003)

Jian Yuan, Russell P Hughes, Arnold L Rheingold

Affiliations

  1. Department of Chemistry, 6128 Burke Laboratory, Dartmouth College, Hanover, New Hampshire 03755, USA. [email protected].

PMID: 26158776 DOI: 10.1039/c5dt02075a

Abstract

The (pentafluoroethyl)(trifluoromethyl)carbene complex Cp*Ir(CO)[[double bond, length as m-dash]C(CF3)(C2F5)] was synthesized by the reductive activation of the α-C-F bond in the perfluoro-sec-butyl-iridium complex Cp*Ir(CO)[CF(CF3)(C2F5)](I) with Na/Pb alloy. This compound exists as two geometric isomers in solution; the structure of one isomer has been determined by a single crystal X-ray diffraction study and contains two independent molecules in the asymmetric unit. Further reduction of this carbene complex with Na/Pb alloy afforded the perfluoro-2-butyne iridium complex Cp*Ir(CO)(η(2)-CF3C[triple bond, length as m-dash]CCF3) by an overall 2-electron reduction and elimination of two β-fluorides. When magnesium graphite was utilized as the reducing agent for the further reduction, Cp*Ir(CO)(η(2)-CF3C[triple bond, length as m-dash]CCF3) was produced as a minor product and the major product was the perfluoroiridacyclobutene complex Cp*Ir(CO)(η(2,4)-CF3CCFCF2) resulting from a γ-C-F bond activation. Direct reduction of the precursor Cp*Ir(CO)[CF(CF3)(C2F5)](i) with magnesium graphite generated the tetrafluorobutatriene iridium complex Cp*Ir(CO)(η(2,3)-CF2[double bond, length as m-dash]C[double bond, length as m-dash]C[double bond, length as m-dash]CF2) along with the perfluoro-2-butyne complex and perfluoroiridacyclobutene complexes in a ratio of 1 : 2 : 6. These reductive inner-sphere pathways to unsaturated fluorocarbon ligands illustrate that carbon-fluorine bond activation can take place at α-, β- and γ-carbons but that selectivity in these heterogeneous reductions is difficult to control, with a variety of fluoride eliminations possible for complex perfluoroalkyl ligands. Density Functional Theory (DFT/B3LYP-D3/LACV3P**++) is used to explore the relative energetics of products and intermediates in these reactions.

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