10.1021/ic060318d.s003 Pierre Croizat Pierre Croizat Nicolas Auvray Nicolas Auvray Pierre Braunstein Pierre Braunstein Richard Welter Richard Welter Comparative Bonding Behavior of Functional Cyclopentadienyl Ligands and Boron-Containing Analogues in Heterometallic Complexes and Clusters<sup>†</sup> American Chemical Society 2006 intramolecular contacts Pt 2Cl Heterometallic Complexes building block 2Pd phenyl substituents carbon atoms coordination modes II functionalized cyclopentadienyl ligand clusters influences isolobal molybdenum carbonylmetalates 54 CVE cluster metal cores Comparative Bonding Behavior Functional Cyclopentadienyl Ligands carbonyl groups crystal structure electron donors carbonyl ligands Mo 2006-07-24 00:00:00 Dataset https://acs.figshare.com/articles/dataset/Comparative_Bonding_Behavior_of_Functional_Cyclopentadienyl_Ligands_and_Boron_Containing_Analogues_in_Heterometallic_Complexes_and_Clusters_sup_sup_/3069277 The reactivity of isolobal molybdenum carbonylmetalates containing a 2-boratanaphthalene, [Mo(η<sup>5</sup>-2,4-MeC<sub>9</sub>H<sub>6</sub>BMe)(CO)<sub>3</sub>]<sup>-</sup> (<b>5a</b>) and [Mo(η<sup>5</sup>-2,4-MeC<sub>9</sub>H<sub>6</sub>BN<i>i</i>-Pr<sub>2</sub>)(CO)<sub>3</sub>]<sup>-</sup> (<b>5b</b>), a 1-boratabenzene, [Mo(η<sup>5</sup>-3,5-Me<sub>2</sub>C<sub>5</sub>H<sub>3</sub>BN<i>i</i>-Pr<sub>2</sub>)(CO)<sub>3</sub>]<sup>-</sup> (<b>8</b>)<b>, </b>or a functionalized cyclopentadienyl ligand, the new metalate [Mo(η<sup>5</sup>-C<sub>5</sub>H<sub>4</sub>Ph)(CO)<sub>3</sub>]<sup>-</sup> (<b>7</b>) and [Mo(η<sup>5</sup>-C<sub>5</sub>H<sub>4</sub>NMe<sub>2</sub>)(CO)<sub>3</sub>]<sup>-</sup> (<b>9</b>), toward palladium (I and II) or platinum (I and II) complexes, such as <i>trans-</i>[PdCl<sub>2</sub>(NCPh)<sub>2</sub>], [Pd<sub>2</sub>(NCMe)<sub>6</sub>](BF<sub>4</sub>)<sub>2</sub>, <i>trans-</i>[PtCl<sub>2</sub>(PEt<sub>3</sub>)<sub>2</sub>], and [N(<i>n-</i>Bu)<sub>4</sub>]<sub>2</sub> [Pt<sub>2</sub>Cl<sub>4</sub>(CO)<sub>2</sub>], has been investigated, and this has allowed an evaluation of the influence of the π-bonded ligands on the structures and unprecedented coordination modes observed in the resulting metal−metal-bonded heterometallic clusters. The new 58 CVE planar-triangulated centrosymmetric clusters, [Mo<sub>2</sub>Pd<sub>2</sub>(η<sup>5</sup>-C<sub>5</sub>H<sub>4</sub>Ph)<sub>2</sub>(CO)<sub>6</sub>(PEt<sub>3</sub>)<sub>2</sub>] (<b>11</b>), [Mo<sub>2</sub>Pd<sub>2</sub>(η<sup>5</sup>-2,4-MeC<sub>9</sub>H<sub>6</sub>BN<i>i</i>-Pr<sub>2</sub>)<sub>2</sub>(CO)<sub>6</sub>] (<b>12</b>), [Mo<sub>2</sub>Pd<sub>2</sub>(η<sup>5</sup>-3,5-Me<sub>2</sub>C<sub>5</sub>H<sub>3</sub>BN<i>i-</i>Pr<sub>2</sub>)<sub>2</sub>(CO)<sub>6</sub>] (<b>13</b>), [Mo<sub>2</sub>Pd<sub>2</sub>(η<sup>5</sup>-C<sub>5</sub>H<sub>4</sub>NMe<sub>2</sub>)<sub>2</sub>(CO)<sub>6</sub>(PEt<sub>3</sub>)<sub>2</sub>] (<b>15</b>), [Mo<sub>2</sub>Pt<sub>2</sub>(η<sup>5</sup>-C<sub>5</sub>H<sub>4</sub>NMe<sub>2</sub>)<sub>2</sub>(CO)<sub>6</sub>(PEt<sub>3</sub>)<sub>2</sub>] (<b>16</b>), and [Mo<sub>2</sub>Pt<sub>2</sub>(η<sup>5</sup>-C<sub>5</sub>H<sub>4</sub>NMe<sub>2</sub>)<sub>2</sub>(CO)<sub>8</sub>] (<b>20</b>), have been characterized by single-crystal X-ray diffraction. Their structural features were compared with those of the 54 CVE cluster [Re<sub>2</sub>Pd<sub>2</sub>(η<sup>5</sup>-C<sub>4</sub>H<sub>4</sub>BPh)<sub>2</sub>(CO)<sub>6</sub>)] (<b>4</b>), previously obtained from the borole-containing metalate [Re(η<sup>5</sup>-C<sub>4</sub>H<sub>4</sub>BPh)(CO)<sub>3</sub>]<sup>-</sup> (<b>2</b>), in which a 2e−3c B−C<sub>ipso</sub>−Pd interaction involving the π-ring was observed. As an extension of what has been observed in <b>4</b>, clusters <b>12</b> and <b>13</b> present a direct interaction of the boratanaphthalene (<b>12</b>) and the boratabenzene (<b>13</b>) ligands with palladium. In clusters <b>11</b>, <b>15</b>, <b>16</b>, and <b>20</b>, the π-ring does not interact with the palladium (<b>11</b> and <b>15</b>) or platinum centers (<b>16</b> and <b>20</b>), which confers to these clusters a geometry very similar to that of [Mo<sub>2</sub>Pd<sub>2</sub>(η<sup>5</sup>-C<sub>5</sub>H<sub>5</sub>)<sub>2</sub>(CO)<sub>6</sub>(PEt<sub>3</sub>)<sub>2</sub>] (<b>3b</b>). The carbonylmetalates [Mo(π-ring)(CO)<sub>3</sub>]<sup>-</sup> are thus best viewed as formal four electron donors which bridge a dinuclear d<sup>9</sup>−d<sup>9</sup> unit. The orientation of this building block in the clusters influences the shape of their metal cores and the bonding mode of the bridging carbonyl ligands. The crystal structure of new centrosymmetric complex [Mo(η<sup>5</sup>-C<sub>5</sub>H<sub>4</sub>Ph)(CO)<sub>3</sub>]<sub>2</sub> (<b>10</b>) was determined, and it revealed intramolecular contacts of 2.773(4) Å between the carbon atoms of carbonyl groups across the metal−metal bond and intermolecular bifurcated interactions between the carbonyl oxygen atoms (2.938(4) and 3.029(4) Å), as well as intermolecular C−H···π<sub>Ar</sub>(CC) interactions (2.334(3) and 2.786(4) Å) involving the phenyl substituents.