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Issue 7, 2011
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CCl3+ and CBr3+ salts with the [Al(ORF)4] and [(FRO)3Al–F–Al(ORF)3] anions (RF = C(CF3)3)

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The CX3+ salts [CCl3]+[Al(ORF)4]1, [CCl3]+[(RFO)3Al–F–Al(ORF)3]2, [CBr3]+[Al(ORF)4]3, [CBr3]+[(RFO)3Al–F–Al(ORF)3]4 (RF = C(CF3)3) were prepared in 56 to 85% yield from CX4 (X = Cl, Br) and the corresponding silver salts (weight balance, NMR, IR, X-ray structure of 1). The most convenient solvent for the preparation of 1 and 2 is SO2ClF but for 3 and 4 it is SO2. The reactions are complete after about three days stirring at −30 to −40 °C. The salts are stable for weeks in solution at −40 °C and stable for a few hours at RT in the solid state. In SO2ClF (1, 2) or SO2 (3, 4) solution they decompose slowly at −20 °C and within several hours at RT; in general the CBr3+ salts are more stable than the CCl3+ homologues. The decomposition products were assigned as CCl3F and primarily CBr2F2 (which likely forms as a Lewis acid induced disproportionation product of the initial CBr3F). The C-X vibrations of the salts were found in the expected range and the assignments were made based on experimental and calculated data. The IR spectrum of a CBr3+ salt is for the first time reported here.

Graphical abstract: CCl3+ and CBr3+ salts with the [Al(ORF)4]− and [(FRO)3Al–F–Al(ORF)3]− anions (RF = C(CF3)3)

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Publication details

The article was received on 20 Aug 2010, accepted on 27 Oct 2010 and first published on 03 Dec 2010

Article type: Paper
DOI: 10.1039/C0DT01076F
Citation: Dalton Trans., 2011,40, 1448-1452
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    CCl3+ and CBr3+ salts with the [Al(ORF)4] and [(FRO)3Al–F–Al(ORF)3] anions (RF = C(CF3)3)

    A. J. Lehner, N. Trapp, H. Scherer and I. Krossing, Dalton Trans., 2011, 40, 1448
    DOI: 10.1039/C0DT01076F

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