Unsymmetric Ir<sub>2</sub> and RhIr Dinuclear Complexes Supported by a Linear Tetraphosphine <i>meso</i>-dpmppp, Showing High Reactivity for O<sub>2</sub>, H<sub>2</sub>, and HCl
Unsymmetric dinuclear Ir(I) complexes, [Ir<sub>2</sub>Cl<sub>2</sub>(L)(<i>meso</i>-dpmppp)] (L = XylNC (<b>1aIr</b><sub><b>2</b></sub>), <i><sup>t</sup></i>BuNC (<b>1bIr</b><sub><b>2</b></sub>), CO (<b>1cIr</b><sub><b>2</b></sub>)), were synthesized using <i>meso</i>-Ph<sub>2</sub>PCH<sub>2</sub>P(Ph)(CH<sub>2</sub>)<sub>3</sub>P(Ph)CH<sub>2</sub>PPh<sub>2</sub> (<i>meso</i>-dpmppp), which supports <i>cis</i>-<i>P,P</i> (M<sup>1</sup>) and <i>trans-P,P</i> (M<sup>2</sup>) metal sites, and exhibited high reactivity for O<sub>2</sub>, H<sub>2</sub>, and HCl. The IrRh heterodinuclear complexes, [M<sup>1</sup>M<sup>2</sup>Cl<sub>2</sub>(L)(<i>meso</i>-dpmppp)] (<b>1</b><i><b>x</b></i><b>M</b><sup><b>1</b></sup><b>M</b><sup><b>2</b></sup>) (M<sup>1</sup>M<sup>2</sup> = IrRh, RhIr; L = XylNC, CO (<b><i>x</i></b> = <b>a</b>, <b>c</b>)), were also synthesized and used together with the Rh<sub>2</sub> complexes (<b>1a,cRh</b><sub><b>2</b></sub>) to elucidate the role of each metal site. For the reactions of O<sub>2</sub>, <b>1aIr</b><sub><b>2</b></sub> and <b>1aRhIr</b> showed higher reactivity than those of <b>1aIrRh</b> and <b>1aRh</b><sub><b>2</b></sub>, giving η<sup>2</sup>-peroxide complexes [{M<sup>1</sup>Cl<sub>2</sub>}{M<sup>2</sup>(η<sup>2</sup>-O<sub>2</sub>)(XylNC)}(<i>meso</i>-dpmppp)] (<b>2aIr</b><sub><b>2</b></sub>, <b>2aRhIr</b>), from which O<sub>2</sub> would not dissociate. All the CO complexes <b>1cM</b><sup><b>1</b></sup><b>M</b><sup><b>2</b></sup> (M<sup>1</sup>, M<sup>2</sup> = Ir or Rh) showed no reactivity for O<sub>2</sub>. In the reactions with H<sub>2</sub>, <b>1aIr</b><sub><b>2</b></sub> reacted with H<sub>2</sub> to give the dihydride complex, [{IrCl<sub>2</sub>}{Ir(H)<sub>2</sub>L}(<i>meso</i>-dpmppp)] (<b>11aIr</b><sub><b>2</b></sub>) and the tetrahydride complex, [{Ir(H)Cl<sub>2</sub>}(μ-H){Ir(H)<sub>2</sub>L}(<i>meso</i>-dpmppp)] (<b>12aIr</b><sub><b>2</b></sub>), while <b>1aRhIr</b> gave the dihydride complex, and <b>1aIrRh</b> and <b>1aRh</b><sub><b>2</b></sub> gave no hydride complexes. Reactions of <b>1a,cM</b><sup><b>1</b></sup><b>M</b><sup><b>2</b></sup> with HCl afforded the dihydride complexes, [{IrCl<sub>3</sub>}(μ-H){Ir(H)Cl(XylNC)}(<i>meso</i>-dpmppp)] (<b>14aIr</b><sub><b>2</b></sub>), [{Ir(H)Cl<sub>2</sub>}(μ-H){M<sup>2</sup>Cl<sub>2</sub>(L)}(<i>meso</i>-dpmppp)] (M<sup>2</sup> = Ir, L = CO (<b>15cIr</b><sub><b>2</b></sub>); M<sup>2</sup> = Rh, L = XylNC (<b>15aIrRh</b>), CO (<b>15cIrRh</b>)), and [{Rh(H)Cl<sub>2</sub>}(μ-Cl){Ir(H)Cl(XylNC)}(<i>meso</i>-dpmppp)] (<b>18aRhIr</b>), the structures varying depending on M<sup>1</sup> and M<sup>2</sup> as well as L.
Authors
- Takayuki Nakajima (ORCID: https://orcid.org/0000-0003-3884-9205)
- Tomoaki Tanase (ORCID: https://orcid.org/0000-0003-1838-0112)
- Momoko Kotani
- Kento Iwai (ORCID: https://orcid.org/0000-0002-0923-604X)
- Yuki Maeda (ORCID: https://orcid.org/0009-0009-8089-9231)
- Miwa Sato
Institutions
- Nara Women's University (JP)
Publication Details
- Journal
- Inorganic Chemistry
- Published
- 2024-10-08
- DOI
- https://doi.org/10.1021/acs.inorgchem.4c03241
- Citations
- 1
- Primary Topic
- Organometallic Complex Synthesis and Catalysis
- Type
- article
- Field-Weighted Citation Impact
- 0.25
Funders
- Ministry of Education, Culture, Sports, Science and Technology