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>(CC) interactions (2.334(3) and 2.786(4) Å) involving the phenyl substituents.