Abstract

The mass spectra of the following fluorocarbon derivatives of transition metals have been investigated: (a) the perfluoroalkyl derivatives <i>R<sub>f</sub></i> Mo(CO)<sub>3</sub>C<sub>5</sub>H<sub>5</sub> (<i>R<sub>f</sub></i>=CF<sub>3</sub> and C<sub>3</sub>F<sub>7</sub>); (b) the perfluoroacyl derivatives CF<sub>3</sub>COM (CO)<sub>3</sub>C<sub>5</sub>H<sub>5</sub> (M = Mo and W), C<sub>3</sub>F<sub>7</sub>COM (CO)<sub>3</sub>C<sub>5</sub>H<sub>5</sub> (M = Mo and W), and C<sub>3</sub>F<sub>7</sub>COFe(CO)<sub>2</sub>C<sub>5</sub>H<sub>5</sub>; (c) the perfluoraryl derivatives R<sub>f</sub>Fe(CO)<sub>2</sub>C<sub>5</sub>H<sub>5</sub> (<i>R<sub>f</sub></i> =C<sub>6</sub>F<sub>5</sub>, <i>p</i>-HC<sub>6</sub>F<sub>4</sub>, 3, 4-H<sub>2</sub>C<sub>6</sub>F<sub>3</sub>, and p-CF<sub>3</sub><i>F</i><sub>4</sub>); (d) the hexafluorobutyne derivatives [(CF<sub>3</sub>)<sub>2</sub>C<sub>2</sub>]<sub>3</sub> MNCCH<sub>3</sub> (M = Mo and W); and (e) the bis (trifluoromethyl)tetramethylbicyclo-[2.2,2] octatriene complexes C<sub>14</sub>H<sub>14</sub>F<sub>5</sub>Fe (CO)<sub>3</sub> and C<sub>5</sub>H<sub>5</sub>CoC<sub>14</sub>H<sub>14</sub>F<sub>6</sub>. Unusual features observed in these mass spectra include the following: (a) Evidence for elimination of the neutral metal fluoride fragments FeF<sub>2</sub> and C<sub>5</sub>H<sub>5</sub>CoF; (b) evidence for the elimination of neutral HF and CF<sub>2</sub> fragments; (c) evidence for the elimination of a bridge in the bicyclo [2,2,2] octatriene derivatives; (d) decarbonylation of <i>R</i><sub><i>f</i></sub>COMo(CO)<sub>3</sub>C<sub>5</sub>H<sub>5</sub> compounds, but not their tungsten analogs, in the mass spectrometer; and (e) evidence for the eliminations of C<sub>4</sub>F<sub>4</sub> and CH<sub>3</sub>CN fragments in the mass spectra of the [(CF<sub>3</sub>)<sub>2</sub>C<sub>2</sub>]<sub>3</sub>MNCCH<sub>2</sub> complexes.

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