Osmium- and Iridium-Promoted C–H Bond Activation of 2,2′-Bipyridines and Related Heterocycles: Kinetic and Thermodynamic Preferences

Published on 2020-05-22T22:30:33Z (GMT) by
The <i>d</i><sup>2</sup>-hexahydride complex OsH<sub>6</sub>(P<sup>i</sup>Pr<sub>3</sub>)<sub>2</sub> (<b>1</b>) promotes the activation of C–H bonds of 2,2′-bipyridines and related heterocycles. The study of the same reactions with the deuteride counterpart OsD<sub>6</sub>(P<sup>i</sup>Pr<sub>3</sub>)<sub>2</sub> (<b>1</b>-<i>d</i>) reveals that the activation of the C–H bonds situated in the sterically less hindered positions is kinetically preferred. However, the isolated products are the result of the thermodynamic control of the reactions. Thus, reactions of <b>1</b> with 2,2′-bipyridine, 6-phenyl-2,2′-bipyridine, and 6-methyl-2,2′-bipyridine give the “rollover cyclometalation” products OsH<sub>3</sub>{κ<sup>2</sup>-<i>C</i>,<i>N</i>-[C<sub>5</sub>(R)­H<sub>2</sub>N-py]}­(P<sup>i</sup>Pr<sub>3</sub>)<sub>2</sub> (R = H (<b>2</b>), Ph (<b>3</b>), Me (<b>4</b>)), whereas 3,5-dimethyl-6-phenyl-2,2′-bipyridine affords OsH<sub>2</sub>{κ<sup>3</sup>-<i>C</i>,<i>N</i>,<i>C</i>-[C<sub>5</sub>H<sub>3</sub>N-(Me)<sub>2</sub>py-C<sub>5</sub>H<sub>4</sub>]}­(P<sup>i</sup>Pr<sub>3</sub>)<sub>2</sub> (<b>5</b>), containing a dianionic C,N,C-pincer ligand. The behavior of substrates pyridyl-benzimidazolium and -imidazolium is similar. Reaction of <b>1</b> with 3-methyl-1-(6-phenylpyridin-2-yl)-1<i>H</i>-benzimidazolium tetrafluoroborate leads to OsH<sub>3</sub>{κ<sup>2</sup>-<i>C</i>,<i>C</i>-[MeBzim-C<sub>5</sub>(Ph)­H<sub>2</sub>N]}­(P<sup>i</sup>Pr<sub>3</sub>)<sub>2</sub> (<b>6</b>), bearing an anionic C<sub>py</sub>,C<sub>NHC</sub>-chelate. On the other hand, 3-methyl-1-(6-phenylpyridin-2-yl)-1<i>H</i>-imidazolium tetrafluoroborate yields [OsH<sub>2</sub>{κ<sup>3</sup>-<i>C</i>,<i>N</i>,<i>C</i>-(MeIm-py-C<sub>6</sub>H<sub>4</sub>)}­(P<sup>i</sup>Pr<sub>3</sub>)<sub>2</sub>]­BF<sub>4</sub> (<b>7</b>), containing a monoanionic C,N,C-pincer with a NHC-unit coordinated in an abnormal fashion. The reactivity pattern of these substrates is also observed with the <i>d</i><sup>4</sup>-iridium-pentahydride IrH<sub>5</sub>(P<sup>i</sup>Pr<sub>3</sub>)<sub>2</sub> (<b>8</b>), which has generated IrH<sub>2</sub>{κ<sup>2</sup>-<i>C</i>,<i>N</i>-[C<sub>5</sub>(R)­H<sub>2</sub>N-py]}­(P<sup>i</sup>Pr<sub>3</sub>)<sub>2</sub> (R = H, (<b>9</b>), Ph (<b>10</b>)) and IrH­{κ<sup>3</sup>-<i>C</i>,<i>N</i>,<i>C</i>-[C<sub>5</sub>H<sub>3</sub>N-(Me<sub>2</sub>)­py-C<sub>5</sub>H<sub>4</sub>]}­(P<sup>i</sup>Pr<sub>3</sub>)<sub>2</sub> (<b>11</b>). The osmium­(IV)–carbon bonds display a higher degree of covalency than the iridium­(III)–carbon bonds. In contrast to <b>2</b>, the metalated carbon atom of <b>9</b> undergoes the addition of a proton of methanol to give [IrH<sub>2</sub>{κ<sup>2</sup>-<i>N</i>,<i>N</i>-(bipy)}­(P<sup>i</sup>Pr<sub>3</sub>)<sub>2</sub>]­BF<sub>4</sub> (<b>12</b>).

Cite this collection

Cancela, Lara; Esteruelas, Miguel A.; López, Ana M.; Oliván, Montserrat; Oñate, Enrique; San-Torcuato, Ainhoa; et al. (2020): Osmium- and Iridium-Promoted C–H Bond Activation

of 2,2′-Bipyridines and Related Heterocycles: Kinetic and Thermodynamic

Preferences. ACS Publications. Collection. https://doi.org/10.1021/acs.organomet.0c00156