Heterolytic cleavage of the B–H bond in H <sub>3</sub> B·L (L = THF, NMe <sub>2</sub> H) by an electrophilic Ir( <scp>iii</scp> ) pincer complex [Ir(H)(PMe <sub>3</sub> )( <sup> <i>t</i> Bu4 </sup> POCOP)][BArF4]

Six- and five-coordinate iridium complexes, [Ir(H)Cl(PMe<sub>3</sub>)(<sup><i>t</i>Bu4</sup>POCOP)] (2) (<sup><i>t</i>Bu4</sup>POCOP = κ<sup>3</sup>-C<sub>6</sub>H<sub>3</sub>-2,6-(OP<sup><i>t</i></sup>Bu<sub>2</sub>)<sub>2</sub>) and [Ir(H)(PMe<sub>3</sub>)(<sup><i>t</i>Bu4</sup>POCOP)][BArF4] (3), respectively, have been synthesized and characterized. The reactivity of the electrophilic 16-electron iridium(III) complex 3 with H<sub>2</sub>, H<sub>3</sub>B·THF, H<sub>3</sub>B·NMe<sub>2</sub>H, and H<sub>3</sub>B·NMe<sub>3</sub> was investigated. The reaction of complex 3 with H<sub>2</sub> resulted in the formation of <i>trans</i>-[Ir(H)(η<sup>2</sup>-H<sub>2</sub>)(PMe<sub>3</sub>)(<sup><i>t</i>Bu4</sup>POCOP)][BArF4] complex 5. Complex 3 was found to activate the B-H bonds in H<sub>3</sub>B·THF and H<sub>3</sub>B·NMe<sub>2</sub>H (DMAB) in a heterolytic fashion. The reaction of complex 3 with H<sub>3</sub>B·THF at 298 K afforded <i>trans</i>-[Ir(H)<sub>2</sub>PMe<sub>3</sub>(<sup><i>t</i>Bu4</sup>POCOP)] complex 6 and a boronium compound, [H<sub>2</sub>B(THF)<sub>2</sub>][BArF4]. Monitoring the reaction from 179 to 298 K by NMR spectroscopy revealed the formation of a σ-borane intermediate, <i>trans</i>-[Ir(H)(η<sup>1</sup>-HBH<sub>2</sub>·THF)PMe<sub>3</sub>(<sup><i>t</i>Bu4</sup>POCOP)][BArF4] (3a-Int), <i>en route</i> to the final products observed at 298 K. The formation of this intermediate species was also investigated by density functional theory (DFT) calculations. The reaction of complex 3 with H<sub>3</sub>B·NMe<sub>2</sub>H at 298 K yielded a mixture of complexes 3 and 5 and a cyclic diborazane [H<sub>2</sub>BNMe<sub>2</sub>]<sub>2</sub>. The reaction was found to proceed <i>via</i> intermediates, a σ-borane complex, <i>trans</i>-[Ir(H)(η<sup>1</sup>-HBH<sub>2</sub>·NMe<sub>2</sub>H)PMe<sub>3</sub>(<sup><i>t</i>Bu4</sup>POCOP)][BArF4] (3b), complex 6, [(NHMe<sub>2</sub>)<sub>2</sub>BH<sub>2</sub>][BArF4], and H<sub>2</sub>BNMe<sub>2</sub>. Complex 3 exhibited no reactivity with H<sub>3</sub>B·NMe<sub>3</sub>.

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Journal
Dalton Transactions
Published
2025-11-24
DOI
https://doi.org/10.1039/d5dt01780g
Primary Topic
Organoboron and organosilicon chemistry
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article
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article

Heterolytic cleavage of the B–H bond in H 3 B·L (L = THF, NMe 2 H) by an electrophilic Ir( iii ) pincer complex [Ir(H)(PMe 3 )( t Bu4 POCOP)][BArF4]

Kumar Vanka, Balaji R. Jagirdar, M. K. Pradhan, Apurba Kumar Pal et al.
Dalton Transactions
Organoboron and organosilicon chemistry
article

Heterolytic cleavage of the B–H bond in H 3 B·L (L = THF, NMe 2 H) by an electrophilic Ir( iii ) pincer complex [Ir(H)(PMe 3 )( t Bu4 POCOP)][BArF4]

Kumar Vanka, Balaji R. Jagirdar, M. K. Pradhan, Apurba Kumar Pal, Zeel Yogeshbhai Surati
article en

Abstract

Six- and five-coordinate iridium complexes, [Ir(H)Cl(PMe<sub>3</sub>)(<sup><i>t</i>Bu4</sup>POCOP)] (2) (<sup><i>t</i>Bu4</sup>POCOP = κ<sup>3</sup>-C<sub>6</sub>H<sub>3</sub>-2,6-(OP<sup><i>t</i></sup>Bu<sub>2</sub>)<sub>2</sub>) and [Ir(H)(PMe<sub>3</sub>)(<sup><i>t</i>Bu4</sup>POCOP)][BArF4] (3), respectively, have been synthesized and characterized. The reactivity of the electrophilic 16-electron iridium(III) complex 3 with H<sub>2</sub>, H<sub>3</sub>B·THF, H<sub>3</sub>B·NMe<sub>2</sub>H, and H<sub>3</sub>B·NMe<sub>3</sub> was investigated. The reaction of complex 3 with H<sub>2</sub> resulted in the formation of <i>trans</i>-[Ir(H)(η<sup>2</sup>-H<sub>2</sub>)(PMe<sub>3</sub>)(<sup><i>t</i>Bu4</sup>POCOP)][BArF4] complex 5. Complex 3 was found to activate the B-H bonds in H<sub>3</sub>B·THF and H<sub>3</sub>B·NMe<sub>2</sub>H (DMAB) in a heterolytic fashion. The reaction of complex 3 with H<sub>3</sub>B·THF at 298 K afforded <i>trans</i>-[Ir(H)<sub>2</sub>PMe<sub>3</sub>(<sup><i>t</i>Bu4</sup>POCOP)] complex 6 and a boronium compound, [H<sub>2</sub>B(THF)<sub>2</sub>][BArF4]. Monitoring the reaction from 179 to 298 K by NMR spectroscopy revealed the formation of a σ-borane intermediate, <i>trans</i>-[Ir(H)(η<sup>1</sup>-HBH<sub>2</sub>·THF)PMe<sub>3</sub>(<sup><i>t</i>Bu4</sup>POCOP)][BArF4] (3a-Int), <i>en route</i> to the final products observed at 298 K. The formation of this intermediate species was also investigated by density functional theory (DFT) calculations. The reaction of complex 3 with H<sub>3</sub>B·NMe<sub>2</sub>H at 298 K yielded a mixture of complexes 3 and 5 and a cyclic diborazane [H<sub>2</sub>BNMe<sub>2</sub>]<sub>2</sub>. The reaction was found to proceed <i>via</i> intermediates, a σ-borane complex, <i>trans</i>-[Ir(H)(η<sup>1</sup>-HBH<sub>2</sub>·NMe<sub>2</sub>H)PMe<sub>3</sub>(<sup><i>t</i>Bu4</sup>POCOP)][BArF4] (3b), complex 6, [(NHMe<sub>2</sub>)<sub>2</sub>BH<sub>2</sub>][BArF4], and H<sub>2</sub>BNMe<sub>2</sub>. Complex 3 exhibited no reactivity with H<sub>3</sub>B·NMe<sub>3</sub>.

Dalton TransactionsVol. 55(1)
National Chemical Laboratory (IN), Indian Institute of Science Bangalore (IN), Academy of Scientific and Innovative Research (IN)
Openalex Percentile: Top 73%
Organoboron and organosilicon chemistry
DOISourceOpenAlex
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