Synthesis and reactivity studies of cationic Ir(III) alkylidines. α-hydride abstraction reactions
The chemistry of late transition metal alkylidenes [M=CR2], where R is H a hydrocarbyl group, have attracted widespread attention although mainly with reference to complexes of metals in low oxidation state. We focus in this paper on reactions based on electrophilic attacks by Ph3C+ that allow eithe...
| Authors: | ; |
|---|---|
| Format: | Article |
| Status: | Submitted version |
| Publication date: | 2017 |
| Country: | España |
| Institution: | Universidad de Sevilla (US) |
| Repository: | idUS. Depósito de Investigación de la Universidad de Sevilla |
| OAI Identifier: | oai:idus.us.es:11441/74582 |
| Online Access: | https://hdl.handle.net/11441/74582 https://doi.org/10.29356/jmcs.v61i2.254 |
| Access Level: | Open access |
| Keyword: | Alkylidene Hydride abstraction Iridium C-C coupling Metalacycle |
| _version_ | 1878738427759820800 |
|---|---|
| author | Campos, Jesús |
| author2 | Carmona Guzmán, Ernesto |
| author2_role | author |
| author_browse | Campos, Jesús Carmona Guzmán, Ernesto |
| author_facet | Campos, Jesús Carmona Guzmán, Ernesto |
| author_role | author |
| collection | idUS. Depósito de Investigación de la Universidad de Sevilla |
| description | The chemistry of late transition metal alkylidenes [M=CR2], where R is H a hydrocarbyl group, have attracted widespread attention although mainly with reference to complexes of metals in low oxidation state. We focus in this paper on reactions based on electrophilic attacks by Ph3C+ that allow either isolation of stable cationic Ir(III) alkylidenes, considerably more attractive than well-known Ir(I) counterparts, or the generation of very reactive variants that experience fast migratory insertion into existing Ir-C and Ir-H sigma bonds. The present studies are based on (η5-C5Me5)Ir(III) complexes that bear a cyclometalated PMeXyl2 ligand (Xyl = 2,6-Me2C6H3). The contribution of different monoanionic ligands (chloride, alkyl or hydride) to either stabilize the Ir=CR2 linkage or provide facile reactivity routes has been investigated, including the use of various deuterium isotopologues of the iridium complex precursors. |
| eu_rights_str_mv | openAccess |
| format | article |
| id | ES_aed4e33abebc5f4d466dcb4c04b09c7f |
| institution | Universidad de Sevilla (US) |
| instname_str | Universidad de Sevilla (US) |
| network_acronym_str | ES |
| network_name_str | España |
| oai_identifier_str | oai:idus.us.es:11441/74582 |
| publishDate | 2017 |
| publishDateSort | 2017 |
| publisher | Sociedad Química de México |
| publisherStr | Sociedad Química de México |
| reponame_str | idUS. Depósito de Investigación de la Universidad de Sevilla |
| spelling | Synthesis and reactivity studies of cationic Ir(III) alkylidines. α-hydride abstraction reactions Campos, Jesús Carmona Guzmán, Ernesto Alkylidene Hydride abstraction Iridium C-C coupling Metalacycle The chemistry of late transition metal alkylidenes [M=CR2], where R is H a hydrocarbyl group, have attracted widespread attention although mainly with reference to complexes of metals in low oxidation state. We focus in this paper on reactions based on electrophilic attacks by Ph3C+ that allow either isolation of stable cationic Ir(III) alkylidenes, considerably more attractive than well-known Ir(I) counterparts, or the generation of very reactive variants that experience fast migratory insertion into existing Ir-C and Ir-H sigma bonds. The present studies are based on (η5-C5Me5)Ir(III) complexes that bear a cyclometalated PMeXyl2 ligand (Xyl = 2,6-Me2C6H3). The contribution of different monoanionic ligands (chloride, alkyl or hydride) to either stabilize the Ir=CR2 linkage or provide facile reactivity routes has been investigated, including the use of various deuterium isotopologues of the iridium complex precursors. Sociedad Química de México https://hdl.handle.net/11441/74582 https://doi.org/10.29356/jmcs.v61i2.254 |
| spellingShingle | Synthesis and reactivity studies of cationic Ir(III) alkylidines. α-hydride abstraction reactions Campos, Jesús Alkylidene Hydride abstraction Iridium C-C coupling Metalacycle |
| status_str | submittedVersion |
| title | Synthesis and reactivity studies of cationic Ir(III) alkylidines. α-hydride abstraction reactions |
| title_full | Synthesis and reactivity studies of cationic Ir(III) alkylidines. α-hydride abstraction reactions |
| title_fullStr | Synthesis and reactivity studies of cationic Ir(III) alkylidines. α-hydride abstraction reactions |
| title_full_unstemmed | Synthesis and reactivity studies of cationic Ir(III) alkylidines. α-hydride abstraction reactions |
| title_short | Synthesis and reactivity studies of cationic Ir(III) alkylidines. α-hydride abstraction reactions |
| title_sort | Synthesis and reactivity studies of cationic Ir(III) alkylidines. α-hydride abstraction reactions |
| topic | Alkylidene Hydride abstraction Iridium C-C coupling Metalacycle |
| topic_facet | Alkylidene Hydride abstraction Iridium C-C coupling Metalacycle |
| url | https://hdl.handle.net/11441/74582 https://doi.org/10.29356/jmcs.v61i2.254 |