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Tri- and Tetranuclear Mixed-Metal Clusters Containing Alkyne Ligands : Synthesis and Structure of [Ru<sub>3</sub>Ir(CO)<sub>11</sub>(RCCR’)]<sup>-</sup>, [Ru<sub>2</sub>Ir(CO)<sub>9</sub>(RCCR’)]<sup>-</sup>, and [HRu<sub>2</sub>Ir(CO)<sub>9</sub>(RCCR’)]
Auteur(s)
Ferrand, Vincent
Neels, Antonia
Date de parution
1999
In
European Journal of Inorganic Chemistry, 1999/5/853 - 862
Résumé
The tetrahedral cluster anion [Ru<sub>3</sub>Ir(CO)<sub>13</sub>]<sup>-</sup> (<b>1</b>) reacts with internal alkynes RCCR to afford the alkyne derivatives [Ru<sub>3</sub>Ir(CO)<sub>11</sub>(RCCR)]<sup>-</sup> (<b>2</b>: R = R’ = Ph; <b>3</b>: R = R’ = Et; <b>4</b>: R = Ph; R’ = Me; <b>5</b>: R = R’ = Me) which have a butterfly arrangement of the Ru<sub>3</sub>Ir skeleton in which the alkyne is coordinated in a μ<sub>4</sub>-η<sup>2</sup> fashion. Under CO pressure they undergo fragmentation to give the trinuclear cluster anions [Ru<sub>2</sub>Ir(CO)<sub>9</sub> (RCCR)]<sup>-</sup> (<b>6</b>: R = R’ = Ph; <b>7</b>: R = R’ = Et; <b>8</b>: R’ = Ph; R’ = Me; <b>9</b>: R = R’ = Me), in which the alkyne ligand is coordinated in a μ<sub>3</sub>-η<sup>2</sup> parallel fashion. Protonation of these trinuclear anions leads to the formation of the corresponding neutral hydrido clusters [HRu<sub>2</sub>Ir(CO)<sub>9</sub> (RCCR)] (<b>10</b>: R = R’ = Ph; <b>11</b>: R = R’ = Et; <b>12</b>: R = Ph; R’ = Me; <b>13</b>: R = R’ = Me). The protonation of the butterfly anions <b>2</b> and <b>3</b>, however, gives rise to the formation of the neutral tetrahedral clusters [HRu<sub>3</sub>Ir(CO)<sub>11</sub>(RCCR)] (<b>14</b>: R = R’ = Ph and <b>15</b>: R = R’ = Et), respectively. The analogous clusters [HRu<sub>3</sub>Ir(CO)<sub>11</sub>(PhCCCH<sub>3</sub>)] (<b>16</b>) and [HRu<sub>3</sub>Ir(CO)<sub>11</sub>(CH<sub>3</sub>CCCH<sub>3</sub>)] (<b>17</b>) are only accessible from the reaction of the neutral cluster [HRu<sub>3</sub>Ir(CO)<sub>13</sub>] with the corresponding alkynes. The complexes <b>2</b>, <b>4</b>, <b>5</b>, <b>6</b>, <b>10</b>, <b>12</b> and <b>15</b> are characterised by X-ray structure analysis.
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Type de publication
journal article
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