Cationic iridium phosphines partnered with [closo-CB11H6Br6](_): (PPh3)(2)Ir(H)(2)(closo-CB11H6Br6) and [(PPh3)(2)Ir(eta(2)-C2H4)(3)][closo-CB11H6Br6]. Relevance to counterion effects in olefin hydrogenation
Treatment of [(PPh3)2Ir(COD)][closo-CB11H6 Br6] with H2 in CH2Cl2 solution affords crystallographically characterized (PPh3)2Ir(H)2(closo-CB11 H6Br6), in which the weakly coordinating carborane anion is bound to the metal center. In solution the anion rapidly dissociates/recombines with the metal ce...
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| Format: | Journal article |
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2004
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| _version_ | 1797054599715094528 |
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| author | Rifat, A Kociok-Kohn, G Steed, J Weller, A |
| author_facet | Rifat, A Kociok-Kohn, G Steed, J Weller, A |
| author_sort | Rifat, A |
| collection | OXFORD |
| description | Treatment of [(PPh3)2Ir(COD)][closo-CB11H6 Br6] with H2 in CH2Cl2 solution affords crystallographically characterized (PPh3)2Ir(H)2(closo-CB11 H6Br6), in which the weakly coordinating carborane anion is bound to the metal center. In solution the anion rapidly dissociates/recombines with the metal center, and this process can be frozen out at -50°C. At lower temperatures (-80°C) a solvent-stabilized complex [(PPh3)2Ir(H)2 (CH2Cl2)][closo-CB11H6Br6 ] is suggested to also be present. (PPh3)2Ir(H)2(closo-CB11 H6Br6) reacts with ethene to give the tris-ethene complex [(PPh3)2Ir(η2-C2 H4)3] [closo-CB11H6Br6]. Subsequent addition of hydrogen returns (PPh3)2Ir(H)2(closo-CB11 H6Br6). This cycle can be repeated a number of times without apparent decomposition, with the anion acting in a "catch and release" manner, stabilizing the metal center when needed. This stabilization is also apparent for the hydrogenation of cyclohexene with (PPh3)2Ir(H)2(closo-CB11 H6Br6) as a catalyst. The complex may be reused up to five times, without decomposition to di- and trimeric iridium hydride species. This is in contrast to other reported iridium hydrogenation systems with other weakly coordinating anions that, on consumption of olefin, decompose to inactive complexes. The new complexes reported here represent intermediates in the catalytic cycle of olefin hydrogenation by cationic group 9 catalysts. |
| first_indexed | 2024-03-06T18:59:28Z |
| format | Journal article |
| id | oxford-uuid:1304df12-b6d0-435a-baad-419f9ed10795 |
| institution | University of Oxford |
| last_indexed | 2024-03-06T18:59:28Z |
| publishDate | 2004 |
| record_format | dspace |
| spelling | oxford-uuid:1304df12-b6d0-435a-baad-419f9ed107952022-03-26T10:11:25ZCationic iridium phosphines partnered with [closo-CB11H6Br6](_): (PPh3)(2)Ir(H)(2)(closo-CB11H6Br6) and [(PPh3)(2)Ir(eta(2)-C2H4)(3)][closo-CB11H6Br6]. Relevance to counterion effects in olefin hydrogenationJournal articlehttp://purl.org/coar/resource_type/c_dcae04bcuuid:1304df12-b6d0-435a-baad-419f9ed10795Symplectic Elements at Oxford2004Rifat, AKociok-Kohn, GSteed, JWeller, ATreatment of [(PPh3)2Ir(COD)][closo-CB11H6 Br6] with H2 in CH2Cl2 solution affords crystallographically characterized (PPh3)2Ir(H)2(closo-CB11 H6Br6), in which the weakly coordinating carborane anion is bound to the metal center. In solution the anion rapidly dissociates/recombines with the metal center, and this process can be frozen out at -50°C. At lower temperatures (-80°C) a solvent-stabilized complex [(PPh3)2Ir(H)2 (CH2Cl2)][closo-CB11H6Br6 ] is suggested to also be present. (PPh3)2Ir(H)2(closo-CB11 H6Br6) reacts with ethene to give the tris-ethene complex [(PPh3)2Ir(η2-C2 H4)3] [closo-CB11H6Br6]. Subsequent addition of hydrogen returns (PPh3)2Ir(H)2(closo-CB11 H6Br6). This cycle can be repeated a number of times without apparent decomposition, with the anion acting in a "catch and release" manner, stabilizing the metal center when needed. This stabilization is also apparent for the hydrogenation of cyclohexene with (PPh3)2Ir(H)2(closo-CB11 H6Br6) as a catalyst. The complex may be reused up to five times, without decomposition to di- and trimeric iridium hydride species. This is in contrast to other reported iridium hydrogenation systems with other weakly coordinating anions that, on consumption of olefin, decompose to inactive complexes. The new complexes reported here represent intermediates in the catalytic cycle of olefin hydrogenation by cationic group 9 catalysts. |
| spellingShingle | Rifat, A Kociok-Kohn, G Steed, J Weller, A Cationic iridium phosphines partnered with [closo-CB11H6Br6](_): (PPh3)(2)Ir(H)(2)(closo-CB11H6Br6) and [(PPh3)(2)Ir(eta(2)-C2H4)(3)][closo-CB11H6Br6]. Relevance to counterion effects in olefin hydrogenation |
| title | Cationic iridium phosphines partnered with [closo-CB11H6Br6](_): (PPh3)(2)Ir(H)(2)(closo-CB11H6Br6) and [(PPh3)(2)Ir(eta(2)-C2H4)(3)][closo-CB11H6Br6]. Relevance to counterion effects in olefin hydrogenation |
| title_full | Cationic iridium phosphines partnered with [closo-CB11H6Br6](_): (PPh3)(2)Ir(H)(2)(closo-CB11H6Br6) and [(PPh3)(2)Ir(eta(2)-C2H4)(3)][closo-CB11H6Br6]. Relevance to counterion effects in olefin hydrogenation |
| title_fullStr | Cationic iridium phosphines partnered with [closo-CB11H6Br6](_): (PPh3)(2)Ir(H)(2)(closo-CB11H6Br6) and [(PPh3)(2)Ir(eta(2)-C2H4)(3)][closo-CB11H6Br6]. Relevance to counterion effects in olefin hydrogenation |
| title_full_unstemmed | Cationic iridium phosphines partnered with [closo-CB11H6Br6](_): (PPh3)(2)Ir(H)(2)(closo-CB11H6Br6) and [(PPh3)(2)Ir(eta(2)-C2H4)(3)][closo-CB11H6Br6]. Relevance to counterion effects in olefin hydrogenation |
| title_short | Cationic iridium phosphines partnered with [closo-CB11H6Br6](_): (PPh3)(2)Ir(H)(2)(closo-CB11H6Br6) and [(PPh3)(2)Ir(eta(2)-C2H4)(3)][closo-CB11H6Br6]. Relevance to counterion effects in olefin hydrogenation |
| title_sort | cationic iridium phosphines partnered with closo cb11h6br6 pph3 2 ir h 2 closo cb11h6br6 and pph3 2 ir eta 2 c2h4 3 closo cb11h6br6 relevance to counterion effects in olefin hydrogenation |
| work_keys_str_mv | AT rifata cationiciridiumphosphinespartneredwithclosocb11h6br6pph32irh2closocb11h6br6andpph32ireta2c2h43closocb11h6br6relevancetocounterioneffectsinolefinhydrogenation AT kociokkohng cationiciridiumphosphinespartneredwithclosocb11h6br6pph32irh2closocb11h6br6andpph32ireta2c2h43closocb11h6br6relevancetocounterioneffectsinolefinhydrogenation AT steedj cationiciridiumphosphinespartneredwithclosocb11h6br6pph32irh2closocb11h6br6andpph32ireta2c2h43closocb11h6br6relevancetocounterioneffectsinolefinhydrogenation AT wellera cationiciridiumphosphinespartneredwithclosocb11h6br6pph32irh2closocb11h6br6andpph32ireta2c2h43closocb11h6br6relevancetocounterioneffectsinolefinhydrogenation |