Triazolyl-phosphole and triazolyl-azaphosphole: synthesis, transition metal complexes and catalytic studies

Phosphole and azaphosphole derivatives with triazole functionalities, [C<sub>6</sub>H<sub>5</sub>{1,2,3-N<sub>3</sub>CC<sub>6</sub>H<sub>4</sub>C(PPh)}] (L1) and [C<sub>6</sub>H<sub>4</sub>{1,2,3-N<sub>3</sub>C(Ph)C(PPh)}] (L2) were synthesized by reacting [(C<sub>6</sub>H<sub>5</sub>)(1,2,3-N<sub>3</sub>C = CH-<i>o</i>-Br-C<sub>6</sub>H<sub>4</sub>)] and [(<i>o</i>-Br-C<sub>6</sub>H<sub>4</sub>)(1,2,3-N<sub>3</sub>C = CHC<sub>6</sub>H<sub>5</sub>)] with <sup><i>n</i></sup>BuLi followed by the addition of dichlorophenylphosphine. The reactions of L1 and L2 with an excess of 30% H<sub>2</sub>O<sub>2</sub> afforded phosphole oxides [C<sub>6</sub>H<sub>5</sub>{1,2,3-N<sub>3</sub>CC<sub>6</sub>H<sub>4</sub>C(P(O)Ph)}] (L1O) and [C<sub>6</sub>H<sub>4</sub>{1,2,3-N<sub>3</sub>C(Ph)C(P(O)Ph)}] (L2O) as white crystalline solids. Stoichiometric reactions of L1 and L2 with [Ru(η<sup>6</sup>-<i>p</i>-cymene)Cl<sub>2</sub>]<sub>2</sub> in CH<sub>2</sub>Cl<sub>2</sub> yielded [RuCl<sub>2</sub>(η<sup>6</sup>-<i>p</i>-cymene)(L1-κ<sup>1</sup>-<i>P</i>)] (1) and [RuCl<sub>2</sub>(η<sup>6</sup>-<i>p</i>-cymene)(L2-κ<sup>1</sup>-<i>P</i>)] (2), respectively. Similar reactions of L1 and L2 with [Pd(COD)Cl<sub>2</sub>] and [Pd(η<sup>3</sup>-C<sub>3</sub>H<sub>5</sub>)Cl]<sub>2</sub> produced the corresponding complexes, <i>trans</i>-[PdCl<sub>2</sub>(L1-κ<sup>1</sup>-<i>P</i>)<sub>2</sub>] (3), <i>trans</i>-[PdCl<sub>2</sub>(L2-κ<sup>1</sup>-<i>P</i>)<sub>2</sub>] (4), [Pd(η<sup>3</sup>-C<sub>3</sub>H<sub>5</sub>)Cl(L1-κ<sup>1</sup>-<i>P</i>)] (5), and [Pd(η<sup>3</sup>-C<sub>3</sub>H<sub>5</sub>)Cl(L2-κ<sup>1</sup>-<i>P</i>)] (6). Treatment of L1 with [AuCl(SMe<sub>2</sub>)] in dichloromethane afforded [AuCl(L1-κ<sup>1</sup>-<i>P</i>)] (7). Ruthenium complex 1 showed moderate to good catalytic activity towards benzylic C-H oxidation, and the proposed mechanism for the catalysis was supported by spectroscopic data.

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Journal
Dalton Transactions
Published
2024-12-27
DOI
https://doi.org/10.1039/d4dt03213f
Primary Topic
Organophosphorus compounds synthesis
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article
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article

Triazolyl-phosphole and triazolyl-azaphosphole: synthesis, transition metal complexes and catalytic studies

Latchupatula Radhakrishna, Maravanji S. Balakrishna, Ankit Kumar Pandey, Basvaraj S. Kote et al.
Dalton Transactions
Organophosphorus compounds synthesis
article

Triazolyl-phosphole and triazolyl-azaphosphole: synthesis, transition metal complexes and catalytic studies

Latchupatula Radhakrishna, Maravanji S. Balakrishna, Ankit Kumar Pandey, Basvaraj S. Kote, Rani Gourkhede, Bhupinder Kaur
article en

Abstract

Phosphole and azaphosphole derivatives with triazole functionalities, [C<sub>6</sub>H<sub>5</sub>{1,2,3-N<sub>3</sub>CC<sub>6</sub>H<sub>4</sub>C(PPh)}] (L1) and [C<sub>6</sub>H<sub>4</sub>{1,2,3-N<sub>3</sub>C(Ph)C(PPh)}] (L2) were synthesized by reacting [(C<sub>6</sub>H<sub>5</sub>)(1,2,3-N<sub>3</sub>C = CH-<i>o</i>-Br-C<sub>6</sub>H<sub>4</sub>)] and [(<i>o</i>-Br-C<sub>6</sub>H<sub>4</sub>)(1,2,3-N<sub>3</sub>C = CHC<sub>6</sub>H<sub>5</sub>)] with <sup><i>n</i></sup>BuLi followed by the addition of dichlorophenylphosphine. The reactions of L1 and L2 with an excess of 30% H<sub>2</sub>O<sub>2</sub> afforded phosphole oxides [C<sub>6</sub>H<sub>5</sub>{1,2,3-N<sub>3</sub>CC<sub>6</sub>H<sub>4</sub>C(P(O)Ph)}] (L1O) and [C<sub>6</sub>H<sub>4</sub>{1,2,3-N<sub>3</sub>C(Ph)C(P(O)Ph)}] (L2O) as white crystalline solids. Stoichiometric reactions of L1 and L2 with [Ru(η<sup>6</sup>-<i>p</i>-cymene)Cl<sub>2</sub>]<sub>2</sub> in CH<sub>2</sub>Cl<sub>2</sub> yielded [RuCl<sub>2</sub>(η<sup>6</sup>-<i>p</i>-cymene)(L1-κ<sup>1</sup>-<i>P</i>)] (1) and [RuCl<sub>2</sub>(η<sup>6</sup>-<i>p</i>-cymene)(L2-κ<sup>1</sup>-<i>P</i>)] (2), respectively. Similar reactions of L1 and L2 with [Pd(COD)Cl<sub>2</sub>] and [Pd(η<sup>3</sup>-C<sub>3</sub>H<sub>5</sub>)Cl]<sub>2</sub> produced the corresponding complexes, <i>trans</i>-[PdCl<sub>2</sub>(L1-κ<sup>1</sup>-<i>P</i>)<sub>2</sub>] (3), <i>trans</i>-[PdCl<sub>2</sub>(L2-κ<sup>1</sup>-<i>P</i>)<sub>2</sub>] (4), [Pd(η<sup>3</sup>-C<sub>3</sub>H<sub>5</sub>)Cl(L1-κ<sup>1</sup>-<i>P</i>)] (5), and [Pd(η<sup>3</sup>-C<sub>3</sub>H<sub>5</sub>)Cl(L2-κ<sup>1</sup>-<i>P</i>)] (6). Treatment of L1 with [AuCl(SMe<sub>2</sub>)] in dichloromethane afforded [AuCl(L1-κ<sup>1</sup>-<i>P</i>)] (7). Ruthenium complex 1 showed moderate to good catalytic activity towards benzylic C-H oxidation, and the proposed mechanism for the catalysis was supported by spectroscopic data.

Dalton TransactionsVol. 54(6)
Indian Institute of Technology Bombay (IN)
Indian Institute of Technology Bombay
Openalex Percentile: Top 82%
Organophosphorus compounds synthesis
DOIOpen Access PDFOpenAlex
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