Activation of Small Molecules by the Metal-Amido Bond of Rhodium(III) and Iridium(III) (η5-C5Me5)M-Aminopyridinate Complexes
We report the synthesis and structural characterization of five-coordinate complexes of rhodium and iridium of the type [(η5-C5Me5)M(N^N)]+ (3-M+), where N^N represents the aminopyridinate ligand derived from 2-NH(Ph)-6-(Xyl)C5H3N (Xyl = 2,6-Me2C6H3). The two complexes were isolated as salts of the...
| Autores: | , , , , |
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| Tipo de recurso: | artículo |
| Estado: | Versión enviada para evaluación y publicación |
| Fecha de publicación: | 2018 |
| País: | España |
| Institución: | Universidad de Sevilla (US) |
| Repositorio: | idUS. Depósito de Investigación de la Universidad de Sevilla |
| OAI Identifier: | oai:idus.us.es:11441/87894 |
| Acceso en línea: | https://hdl.handle.net/11441/87894 https://doi.org/10.1021/acs.inorgchem.7b02283 |
| Access Level: | acceso abierto |
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Activation of Small Molecules by the Metal-Amido Bond of Rhodium(III) and Iridium(III) (η5-C5Me5)M-Aminopyridinate ComplexesZamorano Márquez, AnaRendón Márquez, NuriaLópez Serrano, JoaquínÁlvarez González, EleuterioCarmona Guzmán, ErnestoWe report the synthesis and structural characterization of five-coordinate complexes of rhodium and iridium of the type [(η5-C5Me5)M(N^N)]+ (3-M+), where N^N represents the aminopyridinate ligand derived from 2-NH(Ph)-6-(Xyl)C5H3N (Xyl = 2,6-Me2C6H3). The two complexes were isolated as salts of the BArF anion (BArF = B[3,5-(CF3)2C6H3]4). The M-Namido bond of complexes 3-M+ readily activated CO, C2H4, and H2. Thus, compounds 3-M+ reacted with CO under ambient conditions, but whereas for 3-Rh+, CO migratory insertion was fast, yielding a carbamoyl carbonyl species, 4-Rh+, the stronger Ir-Namido bond of complex 3-Ir+ caused the reaction to stop at the CO coordination stage. In contrast, 3-Ir+ reacted reversibly with C2H4, forming adduct 5-Ir+, which subsequently rearranged irreversibly to [Ir](H)(=C(Me)N(Ph)-) complex 6-Ir+, which contains an N-stabilized carbene ligand. Computational studies supported a migratory insertion mechanism, giving first a β-stabilized linear alkyl unit, [Ir]CH2CH2N(Ph)-, followed by a multistep rearrangement that led to the final product 6-Ir+. Both β- and α-H eliminations, as well as their microscopic reverse migratory insertion reactions, were implicated in the alkyl-to-hydride-carbene reorganization. The analogous reaction of 3-Rh+ with C2H4 originated a complex mixture of products from which only a branched alkyl [Rh]C(H)(Me)N(Ph)- (5-Rh+) could be isolated, featuring a β-agostic methyl interaction. Reactions of 3-M+ with H2 promoted a catalytic isomerization of the Ap ligand from classical κ2-N,N′ binding to κ-N plus η3-pseudoallyl coordination mode.Ministerio de Economía y Competitividad CTQ2016-80814-R, CTQ2016-75193-P, CTQ2016-81797-REDCJunta de Andalucía FQM-119American Chemical SocietyQuímica Inorgánica2018info:eu-repo/semantics/articleinfo:eu-repo/semantics/submittedVersionapplication/pdfapplication/pdfhttps://hdl.handle.net/11441/87894https://doi.org/10.1021/acs.inorgchem.7b02283reponame:idUS. Depósito de Investigación de la Universidad de Sevillainstname:Universidad de Sevilla (US)InglésInorganic Chemistry, 57 (1), 150-162.CTQ2016-80814-RCTQ2016-75193-PCTQ2016-81797-REDCFQM-119http://dx.doi.org/10.1021/acs.inorgchem.7b02283info:eu-repo/semantics/openAccessoai:idus.us.es:11441/878942026-06-17T12:51:07Z |
| dc.title.none.fl_str_mv |
Activation of Small Molecules by the Metal-Amido Bond of Rhodium(III) and Iridium(III) (η5-C5Me5)M-Aminopyridinate Complexes |
| title |
Activation of Small Molecules by the Metal-Amido Bond of Rhodium(III) and Iridium(III) (η5-C5Me5)M-Aminopyridinate Complexes |
| spellingShingle |
Activation of Small Molecules by the Metal-Amido Bond of Rhodium(III) and Iridium(III) (η5-C5Me5)M-Aminopyridinate Complexes Zamorano Márquez, Ana |
| title_short |
Activation of Small Molecules by the Metal-Amido Bond of Rhodium(III) and Iridium(III) (η5-C5Me5)M-Aminopyridinate Complexes |
| title_full |
Activation of Small Molecules by the Metal-Amido Bond of Rhodium(III) and Iridium(III) (η5-C5Me5)M-Aminopyridinate Complexes |
| title_fullStr |
Activation of Small Molecules by the Metal-Amido Bond of Rhodium(III) and Iridium(III) (η5-C5Me5)M-Aminopyridinate Complexes |
| title_full_unstemmed |
Activation of Small Molecules by the Metal-Amido Bond of Rhodium(III) and Iridium(III) (η5-C5Me5)M-Aminopyridinate Complexes |
| title_sort |
Activation of Small Molecules by the Metal-Amido Bond of Rhodium(III) and Iridium(III) (η5-C5Me5)M-Aminopyridinate Complexes |
| dc.creator.none.fl_str_mv |
Zamorano Márquez, Ana Rendón Márquez, Nuria López Serrano, Joaquín Álvarez González, Eleuterio Carmona Guzmán, Ernesto |
| author |
Zamorano Márquez, Ana |
| author_facet |
Zamorano Márquez, Ana Rendón Márquez, Nuria López Serrano, Joaquín Álvarez González, Eleuterio Carmona Guzmán, Ernesto |
| author_role |
author |
| author2 |
Rendón Márquez, Nuria López Serrano, Joaquín Álvarez González, Eleuterio Carmona Guzmán, Ernesto |
| author2_role |
author author author author |
| dc.contributor.none.fl_str_mv |
Química Inorgánica |
| description |
We report the synthesis and structural characterization of five-coordinate complexes of rhodium and iridium of the type [(η5-C5Me5)M(N^N)]+ (3-M+), where N^N represents the aminopyridinate ligand derived from 2-NH(Ph)-6-(Xyl)C5H3N (Xyl = 2,6-Me2C6H3). The two complexes were isolated as salts of the BArF anion (BArF = B[3,5-(CF3)2C6H3]4). The M-Namido bond of complexes 3-M+ readily activated CO, C2H4, and H2. Thus, compounds 3-M+ reacted with CO under ambient conditions, but whereas for 3-Rh+, CO migratory insertion was fast, yielding a carbamoyl carbonyl species, 4-Rh+, the stronger Ir-Namido bond of complex 3-Ir+ caused the reaction to stop at the CO coordination stage. In contrast, 3-Ir+ reacted reversibly with C2H4, forming adduct 5-Ir+, which subsequently rearranged irreversibly to [Ir](H)(=C(Me)N(Ph)-) complex 6-Ir+, which contains an N-stabilized carbene ligand. Computational studies supported a migratory insertion mechanism, giving first a β-stabilized linear alkyl unit, [Ir]CH2CH2N(Ph)-, followed by a multistep rearrangement that led to the final product 6-Ir+. Both β- and α-H eliminations, as well as their microscopic reverse migratory insertion reactions, were implicated in the alkyl-to-hydride-carbene reorganization. The analogous reaction of 3-Rh+ with C2H4 originated a complex mixture of products from which only a branched alkyl [Rh]C(H)(Me)N(Ph)- (5-Rh+) could be isolated, featuring a β-agostic methyl interaction. Reactions of 3-M+ with H2 promoted a catalytic isomerization of the Ap ligand from classical κ2-N,N′ binding to κ-N plus η3-pseudoallyl coordination mode. |
| publishDate |
2018 |
| dc.date.none.fl_str_mv |
2018 |
| dc.type.none.fl_str_mv |
info:eu-repo/semantics/article info:eu-repo/semantics/submittedVersion |
| format |
article |
| status_str |
submittedVersion |
| dc.identifier.none.fl_str_mv |
https://hdl.handle.net/11441/87894 https://doi.org/10.1021/acs.inorgchem.7b02283 |
| url |
https://hdl.handle.net/11441/87894 https://doi.org/10.1021/acs.inorgchem.7b02283 |
| dc.language.none.fl_str_mv |
Inglés |
| language_invalid_str_mv |
Inglés |
| dc.relation.none.fl_str_mv |
Inorganic Chemistry, 57 (1), 150-162. CTQ2016-80814-R CTQ2016-75193-P CTQ2016-81797-REDC FQM-119 http://dx.doi.org/10.1021/acs.inorgchem.7b02283 |
| dc.rights.none.fl_str_mv |
info:eu-repo/semantics/openAccess |
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openAccess |
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application/pdf application/pdf |
| dc.publisher.none.fl_str_mv |
American Chemical Society |
| publisher.none.fl_str_mv |
American Chemical Society |
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reponame:idUS. Depósito de Investigación de la Universidad de Sevilla instname:Universidad de Sevilla (US) |
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Universidad de Sevilla (US) |
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idUS. Depósito de Investigación de la Universidad de Sevilla |
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idUS. Depósito de Investigación de la Universidad de Sevilla |
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15.301603 |