Reactivity of Arenes, Cycloheptatriene, and Dicyclopentadiene with a Basal Edge-Bridged Square Pyramidal Hexaruthenium Dihydride Javier A. Cabeza Ignacio del Río Pablo García-Álvarez Daniel Miguel 10.1021/om060153g.s001 https://acs.figshare.com/articles/dataset/Reactivity_of_Arenes_Cycloheptatriene_and_Dicyclopentadiene_with_a_Basal_Edge_Bridged_Square_Pyramidal_Hexaruthenium_Dihydride/3223861 The reactions of the basal edge-bridged square pyramidal hexanuclear cluster [Ru<sub>6</sub>(μ<sub>3</sub>-H)<sub>2</sub>(μ<sub>5</sub>-κ<sup>2</sup>-ampy)(μ-CO)<sub>2</sub>(CO)<sub>14</sub>] (<b>1</b>; H<sub>2</sub>ampy = 2-amino-6-methylpyridine) with arenes at high temperature (>110 °C) give [Ru<sub>6</sub>(μ<sub>3</sub>-H)<sub>2</sub>(μ<sub>5</sub>-κ<sup>2</sup>-ampy)(η<sup>6</sup>-arene)(μ-CO)<sub>2</sub>(CO)<sub>11</sub>] (arene = C<sub>6</sub>H<sub>6</sub> <b>2a</b>, C<sub>6</sub>H<sub>5</sub>Me <b>2b</b>, 1,4-C<sub>6</sub>H<sub>4</sub>Me<sub>2</sub> <b>2c</b>). These complexes result from the substitution of the arene for the three CO ligands of the apical Ru atom of <b>1</b>. Cycloheptatriene reacts with complex <b>1</b> in chlorobenzene at reflux temperature to give a mixture of products from which the hexanuclear cluster complexes [Ru<sub>6</sub>(μ<sub>3</sub>-H)(μ<sub>5</sub>-κ<sup>2</sup>-ampy)(η<sup>5</sup>-C<sub>7</sub>H<sub>9</sub>)(μ<sub>3</sub>-CO)(μ-CO)<sub>2</sub>(CO)<sub>11</sub>] (<b>3</b>), [Ru<sub>6</sub>(μ<sub>3</sub>-H)(μ<sub>5</sub>-κ<sup>2</sup>-ampy)(μ<sub>3</sub>-η<sup>7</sup>-C<sub>7</sub>H<sub>7</sub>)(μ-CO)<sub>2</sub>(CO)<sub>11</sub>] (<b>4</b>), [Ru<sub>6</sub>(μ<sub>5</sub>-κ<sup>2</sup>-ampy)(μ<sub>2</sub>-η<sup>7</sup>-C<sub>7</sub>H<sub>7</sub>)<sub>2</sub>(μ-CO)(CO)<sub>9</sub>] (<b>5</b>), and [Ru<sub>6</sub>(μ<sub>6</sub>-C)(μ<sub>3</sub>-η<sup>7</sup>-C<sub>7</sub>H<sub>7</sub>)<sub>2</sub>(μ-CO)<sub>2</sub>(CO)<sub>8</sub>] (<b>6</b>) have been isolated and characterized. While compound <b>3</b> has a terminal η<sup>5</sup>-cycloheptadienyl ligand, <b>4</b> contains a face-capping η<sup>5</sup>:η<sup>2</sup>-cycloheptatrienyl ligand, and <b>5</b> has two edge-bridging η<sup>4</sup>:η<sup>3</sup>-cycloheptatrienyl ligands. Compound <b>6</b>, a minor product of this reaction, contains an octahedral metallic skeleton with a μ<sub>6</sub>-carbide and two face-capping η<sup>3</sup>:η<sup>2</sup>:η<sup>2</sup>-cycloheptatrienyl ligands. It has been established that the thermolysis of complex <b>3</b> gives <b>4</b> and that complex <b>5</b> arises from the reaction of <b>4</b> with cycloheptatriene. Treatment of dicyclopentadiene with complex <b>1</b> in chlorobenzene at reflux temperature has allowed the isolation of [Ru<sub>2</sub>(η<sup>5</sup>-C<sub>5</sub>H<sub>5</sub>)<sub>2</sub>(μ-CO)<sub>2</sub>(CO)<sub>2</sub>] and three cluster derivatives, [Ru<sub>6</sub>(μ<sub>3</sub>-H)(μ<sub>5</sub>-κ<sup>2</sup>-ampy)(η<sup>5</sup>-C<sub>5</sub>H<sub>5</sub>)(μ<sub>3</sub>-CO)(μ-CO)<sub>2</sub>(CO)<sub>11</sub>] (<b>7</b>), [Ru<sub>6</sub>(μ<sub>3</sub>-H)<sub>2</sub>(μ<sub>5</sub>-κ<sup>2</sup>-ampy)(η<sup>5</sup>-C<sub>5</sub>H<sub>5</sub>)<sub>2</sub>(μ<sub>3</sub>-CO)(μ-CO)(CO)<sub>9</sub>] (<b>8</b>), and [Ru<sub>5</sub>(μ<sub>5</sub>-κ<sup>2</sup>-ampy)(μ<sub>4</sub>-η<sup>4</sup>-C<sub>10</sub>H<sub>10</sub>)(μ-CO)<sub>2</sub>(CO)<sub>10</sub>] (<b>9</b>). Compounds <b>7</b> and <b>8</b> are hexanuclear and contain one and two terminal cyclopentadienyl ligands, respectively. The pentanuclear derivative <b>9</b> features an unprecedented η<sup>2</sup>:η<sup>2</sup>-enyne ligand that derives from the activation of two adjacent H−C(sp<sup>2</sup>) bonds of dicyclopentadiene. With the exception of compounds <b>6</b> and <b>9</b>, the remaining clusters have the same Ru<sub>6</sub>(μ<sub>5</sub>-κ<sup>2</sup>-ampy) framework as compound <b>1</b> and have the apical Ru atom attached to hydrocarbon ligands. 2006-05-08 00:00:00 C 6 H 5 2 2 c cycloheptatrienyl ligands C 7 H 7 reflux temperature terminal η 5 C 5 H 5 H 2 ampy C 6 H 6 2 CO terminal cyclopentadienyl ligands hexanuclear cluster complexes apical Ru atom