2 research outputs found
Diruthenium Naphthalene and Anthracene Complexes Containing a Doubly Linked Dicyclopentadienyl Ligand
No full textThe reaction of <i>cis</i>-{(η<sup>5</sup>-C<sub>5</sub>H<sub>3</sub>)<sub>2</sub>(CMe<sub>2</sub>)<sub>2</sub>}Ru<sub>2</sub>(CO)<sub>4</sub>Br<sub>2</sub> with naphthalene affords
the <i>syn</i>-facial [<i>cis</i>-{(η<sup>5</sup>-C<sub>5</sub>H<sub>3</sub>)<sub>2</sub>(CMe<sub>2</sub>)<sub>2</sub>}Ru<sub>2</sub>(μ-η<sup>6</sup>,η<sup>6</sup>-C<sub>10</sub>H<sub>8</sub>)][OTf]<sub>2</sub>, (<b>2</b><sup><b>2+</b></sup>), a complex that appears to be two electrons
short of the
18-electron rule. Density functional theory (DFT) calculations suggest
that the Ru atoms satisfy their missing valence by a combination of
a weak metal–metal bond and sharing electrons from the central
π bond of the naphthalene. The one-electron reduction of <b>2</b><sup><b>2+</b></sup> yields <b>2</b><sup><b>+</b></sup>, a Class II mixed-valence complex, while the two-electron
reduction of <b>2</b><sup><b>2+</b></sup> causes a hapticity
change from η<sup>6</sup> to η<sup>4</sup> on one of the
naphthalene rings and yields <i>cis</i>-{(η<sup>5</sup>-C<sub>5</sub>H<sub>3</sub>)<sub>2</sub>(CMe<sub>2</sub>)<sub>2</sub>}Ru<sub>2</sub>(μ-η<sup>6</sup>,η<sup>4</sup>-C<sub>10</sub>H<sub>8</sub><b>)</b> (<b>2</b><sup><b>0</b></sup>), a zwitterionic complex. The DFT calculations predict that
the <i>C</i><sub><i>s</i></sub> isomer of <b>2<sup>0</sup></b> is 4.69 kcal/mol lower in energy than the <i>C</i><sub>2<i>v</i></sub> isomer, which is a transition
state. Reaction of <i>cis</i>-{(η<sup>5</sup>-C<sub>5</sub>H<sub>3</sub>)<sub>2</sub>(CMe<sub>2</sub>)<sub>2</sub>}Ru<sub>2</sub>(CO)<sub>4</sub>Br<sub>2</sub> with anthracene affords the
analogous <i>syn</i>-facial anthracene complex, [<i>cis</i>-{(η<sup>5</sup>-C<sub>5</sub>H<sub>3</sub>)<sub>2</sub>(CMe<sub>2</sub>)<sub>2</sub>}Ru<sub>2</sub>(μ-η<sup>6</sup>,η<sup>6</sup>-C<sub>14</sub>H<sub>10</sub>)][OTf]<sub>2</sub>, (<b>4</b>), and the tetranuclear dianthracene complex,
[<i>cis</i>-{(η<sup>5</sup>-C<sub>5</sub>H<sub>3</sub>)<sub>2</sub>(CMe<sub>2</sub>)<sub>2</sub>}Ru<sub>2</sub>(μ-η<sup>6</sup>,η<sup>6</sup>-C<sub>14</sub>H<sub>10</sub>)]<sub>2</sub>[OTf]<sub>4</sub>, (<b>5</b>). <b>2</b><sup><b>2+</b></sup>, <b>2</b><sup><b>0</b></sup>, and <b>5</b> were structurally characterized by X-ray diffraction
Diruthenium Naphthalene and Anthracene Complexes Containing a Doubly Linked Dicyclopentadienyl Ligand
No full textThe reaction of <i>cis</i>-{(η<sup>5</sup>-C<sub>5</sub>H<sub>3</sub>)<sub>2</sub>(CMe<sub>2</sub>)<sub>2</sub>}Ru<sub>2</sub>(CO)<sub>4</sub>Br<sub>2</sub> with naphthalene affords
the <i>syn</i>-facial [<i>cis</i>-{(η<sup>5</sup>-C<sub>5</sub>H<sub>3</sub>)<sub>2</sub>(CMe<sub>2</sub>)<sub>2</sub>}Ru<sub>2</sub>(μ-η<sup>6</sup>,η<sup>6</sup>-C<sub>10</sub>H<sub>8</sub>)][OTf]<sub>2</sub>, (<b>2</b><sup><b>2+</b></sup>), a complex that appears to be two electrons
short of the
18-electron rule. Density functional theory (DFT) calculations suggest
that the Ru atoms satisfy their missing valence by a combination of
a weak metal–metal bond and sharing electrons from the central
π bond of the naphthalene. The one-electron reduction of <b>2</b><sup><b>2+</b></sup> yields <b>2</b><sup><b>+</b></sup>, a Class II mixed-valence complex, while the two-electron
reduction of <b>2</b><sup><b>2+</b></sup> causes a hapticity
change from η<sup>6</sup> to η<sup>4</sup> on one of the
naphthalene rings and yields <i>cis</i>-{(η<sup>5</sup>-C<sub>5</sub>H<sub>3</sub>)<sub>2</sub>(CMe<sub>2</sub>)<sub>2</sub>}Ru<sub>2</sub>(μ-η<sup>6</sup>,η<sup>4</sup>-C<sub>10</sub>H<sub>8</sub><b>)</b> (<b>2</b><sup><b>0</b></sup>), a zwitterionic complex. The DFT calculations predict that
the <i>C</i><sub><i>s</i></sub> isomer of <b>2<sup>0</sup></b> is 4.69 kcal/mol lower in energy than the <i>C</i><sub>2<i>v</i></sub> isomer, which is a transition
state. Reaction of <i>cis</i>-{(η<sup>5</sup>-C<sub>5</sub>H<sub>3</sub>)<sub>2</sub>(CMe<sub>2</sub>)<sub>2</sub>}Ru<sub>2</sub>(CO)<sub>4</sub>Br<sub>2</sub> with anthracene affords the
analogous <i>syn</i>-facial anthracene complex, [<i>cis</i>-{(η<sup>5</sup>-C<sub>5</sub>H<sub>3</sub>)<sub>2</sub>(CMe<sub>2</sub>)<sub>2</sub>}Ru<sub>2</sub>(μ-η<sup>6</sup>,η<sup>6</sup>-C<sub>14</sub>H<sub>10</sub>)][OTf]<sub>2</sub>, (<b>4</b>), and the tetranuclear dianthracene complex,
[<i>cis</i>-{(η<sup>5</sup>-C<sub>5</sub>H<sub>3</sub>)<sub>2</sub>(CMe<sub>2</sub>)<sub>2</sub>}Ru<sub>2</sub>(μ-η<sup>6</sup>,η<sup>6</sup>-C<sub>14</sub>H<sub>10</sub>)]<sub>2</sub>[OTf]<sub>4</sub>, (<b>5</b>). <b>2</b><sup><b>2+</b></sup>, <b>2</b><sup><b>0</b></sup>, and <b>5</b> were structurally characterized by X-ray diffraction
