Competitive insertion of isocyanide into tantalum-amido and tantalum-methyl bonds
The (amido)methyl complexes [Ta(η5-C5Me5)(NtBu)Me(NR2)] [R = Ph (3), SiMe3 (4)] were prepared by reaction of [Ta(η5-C5Me5)(NtBu)ClMe] (1) with the appropriate lithium amides. Attempts to isolate the analogous NHMe derivative afforded a mixture of complexes [Ta(η5-C5Me5)(NtBu)Me(NHMe)] (5) and [Ta(η5...
| Autores: | , , , , , , , , |
|---|---|
| Tipo de recurso: | artículo |
| Fecha de publicación: | 2002 |
| País: | España |
| Institución: | Universidad de Alcalá (UAH) |
| Repositorio: | e_Buah Biblioteca Digital Universidad de Alcalá |
| Idioma: | inglés |
| OAI Identifier: | oai:ebuah.uah.es:10017/4200 |
| Acceso en línea: | http://hdl.handle.net/10017/4200 https://dx.doi.org/10.1002/1099-0682(200211)2002:11<2810 |
| Access Level: | acceso abierto |
| Palabra clave: | Tantalum Competitive insertion Isocyanide insertion Density functional calculations Ciencia Química inorgánica Science Chemistry, inorganic |
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Competitive insertion of isocyanide into tantalum-amido and tantalum-methyl bondsAmor Chico, Francisco JavierSánchez-Nieves Fernández, Javier|||0000-0003-0410-2285Royo Gracia, PascualJacobsen, HeikoBlacque, OlivierBerke, HeinzLanfranchi, MaurizioPellinghelli, Maria AngelaTiripicchio, AntonioTantalumCompetitive insertionIsocyanide insertionDensity functional calculationsCienciaQuímica inorgánicaScienceChemistry, inorganicThe (amido)methyl complexes [Ta(η5-C5Me5)(NtBu)Me(NR2)] [R = Ph (3), SiMe3 (4)] were prepared by reaction of [Ta(η5-C5Me5)(NtBu)ClMe] (1) with the appropriate lithium amides. Attempts to isolate the analogous NHMe derivative afforded a mixture of complexes [Ta(η5-C5Me5)(NtBu)Me(NHMe)] (5) and [Ta(η5-C5Me5)(NMe)Me(NHtBu)] (6), resulting from hydrogen exchange between the amido and imido ligands. Insertion of CN(2,6-Me2C6H3) into the Ta−Me bond of complexes 3 and 4 gave the η1-iminoacyl derivatives [Ta(η5-C5Me5)(NtBu)(NR2){η1-C(Me)=N(2,6-Me2C6H3)}] [R = Ph (7), SiMe3 (8)], while insertion into the Ta−NRMe (R = H, Me) bond of the complexes [Ta(η5-C5Me5)(NtBu)Me(NRMe)] [R = H (5), Me (2)] gave the η2-iminocarbamoyl compounds [Ta(η5-C5Me5)(NtBu)Me{η2-C(NRMe)=N(2,6-Me2C6H3)}] [R = H (10), Me (9)]. All of the new compounds were characterized by 1H and 13C NMR spectroscopy. The X-ray crystal structure of 9 is reported. DFT calculations were carried out to justify the preference of the insertion either into the Ta−C or the Ta−N bond.Comisión Asesora de Investigación Científica y TécnicaUniversity of ZurichJohn Wiley & Sons20022002-01-01journal articlehttp://purl.org/coar/resource_type/c_6501NAhttp://purl.org/coar/version/c_be7fb7dd8ff6fe43info:eu-repo/semantics/articleapplication/pdfhttp://hdl.handle.net/10017/4200https://dx.doi.org/10.1002/1099-0682(200211)2002:11<2810reponame:e_Buah Biblioteca Digital Universidad de Alcaláinstname:Universidad de Alcalá (UAH)InglésengCAICYT Not available MAT2001-1309 Síntesis y estudio de catalizadores selectivos para la producción de materiales poliolefÍnicos con propiedades predeterminadasopen accesshttp://purl.org/coar/access_right/c_abf2Attribution-NonCommercial-NoDerivatives 4.0 Internationalhttp://creativecommons.org/licenses/by-nc-nd/4.0/info:eu-repo/semantics/openAccessoai:ebuah.uah.es:10017/42002026-06-18T11:13:07Z |
| dc.title.none.fl_str_mv |
Competitive insertion of isocyanide into tantalum-amido and tantalum-methyl bonds |
| title |
Competitive insertion of isocyanide into tantalum-amido and tantalum-methyl bonds |
| spellingShingle |
Competitive insertion of isocyanide into tantalum-amido and tantalum-methyl bonds Amor Chico, Francisco Javier Tantalum Competitive insertion Isocyanide insertion Density functional calculations Ciencia Química inorgánica Science Chemistry, inorganic |
| title_short |
Competitive insertion of isocyanide into tantalum-amido and tantalum-methyl bonds |
| title_full |
Competitive insertion of isocyanide into tantalum-amido and tantalum-methyl bonds |
| title_fullStr |
Competitive insertion of isocyanide into tantalum-amido and tantalum-methyl bonds |
| title_full_unstemmed |
Competitive insertion of isocyanide into tantalum-amido and tantalum-methyl bonds |
| title_sort |
Competitive insertion of isocyanide into tantalum-amido and tantalum-methyl bonds |
| dc.creator.none.fl_str_mv |
Amor Chico, Francisco Javier Sánchez-Nieves Fernández, Javier|||0000-0003-0410-2285 Royo Gracia, Pascual Jacobsen, Heiko Blacque, Olivier Berke, Heinz Lanfranchi, Maurizio Pellinghelli, Maria Angela Tiripicchio, Antonio |
| author |
Amor Chico, Francisco Javier |
| author_facet |
Amor Chico, Francisco Javier Sánchez-Nieves Fernández, Javier|||0000-0003-0410-2285 Royo Gracia, Pascual Jacobsen, Heiko Blacque, Olivier Berke, Heinz Lanfranchi, Maurizio Pellinghelli, Maria Angela Tiripicchio, Antonio |
| author_role |
author |
| author2 |
Sánchez-Nieves Fernández, Javier|||0000-0003-0410-2285 Royo Gracia, Pascual Jacobsen, Heiko Blacque, Olivier Berke, Heinz Lanfranchi, Maurizio Pellinghelli, Maria Angela Tiripicchio, Antonio |
| author2_role |
author author author author author author author author |
| dc.subject.none.fl_str_mv |
Tantalum Competitive insertion Isocyanide insertion Density functional calculations Ciencia Química inorgánica Science Chemistry, inorganic |
| topic |
Tantalum Competitive insertion Isocyanide insertion Density functional calculations Ciencia Química inorgánica Science Chemistry, inorganic |
| description |
The (amido)methyl complexes [Ta(η5-C5Me5)(NtBu)Me(NR2)] [R = Ph (3), SiMe3 (4)] were prepared by reaction of [Ta(η5-C5Me5)(NtBu)ClMe] (1) with the appropriate lithium amides. Attempts to isolate the analogous NHMe derivative afforded a mixture of complexes [Ta(η5-C5Me5)(NtBu)Me(NHMe)] (5) and [Ta(η5-C5Me5)(NMe)Me(NHtBu)] (6), resulting from hydrogen exchange between the amido and imido ligands. Insertion of CN(2,6-Me2C6H3) into the Ta−Me bond of complexes 3 and 4 gave the η1-iminoacyl derivatives [Ta(η5-C5Me5)(NtBu)(NR2){η1-C(Me)=N(2,6-Me2C6H3)}] [R = Ph (7), SiMe3 (8)], while insertion into the Ta−NRMe (R = H, Me) bond of the complexes [Ta(η5-C5Me5)(NtBu)Me(NRMe)] [R = H (5), Me (2)] gave the η2-iminocarbamoyl compounds [Ta(η5-C5Me5)(NtBu)Me{η2-C(NRMe)=N(2,6-Me2C6H3)}] [R = H (10), Me (9)]. All of the new compounds were characterized by 1H and 13C NMR spectroscopy. The X-ray crystal structure of 9 is reported. DFT calculations were carried out to justify the preference of the insertion either into the Ta−C or the Ta−N bond. |
| publishDate |
2002 |
| dc.date.none.fl_str_mv |
2002 2002-01-01 |
| dc.type.none.fl_str_mv |
journal article http://purl.org/coar/resource_type/c_6501 NA http://purl.org/coar/version/c_be7fb7dd8ff6fe43 |
| dc.type.openaire.fl_str_mv |
info:eu-repo/semantics/article |
| format |
article |
| dc.identifier.none.fl_str_mv |
http://hdl.handle.net/10017/4200 https://dx.doi.org/10.1002/1099-0682(200211)2002:11<2810 |
| url |
http://hdl.handle.net/10017/4200 https://dx.doi.org/10.1002/1099-0682(200211)2002:11<2810 |
| dc.language.none.fl_str_mv |
Inglés eng |
| language_invalid_str_mv |
Inglés |
| language |
eng |
| dc.relation.none.fl_str_mv |
CAICYT Not available MAT2001-1309 Síntesis y estudio de catalizadores selectivos para la producción de materiales poliolefÍnicos con propiedades predeterminadas |
| dc.rights.none.fl_str_mv |
open access http://purl.org/coar/access_right/c_abf2 Attribution-NonCommercial-NoDerivatives 4.0 International http://creativecommons.org/licenses/by-nc-nd/4.0/ |
| dc.rights.openaire.fl_str_mv |
info:eu-repo/semantics/openAccess |
| rights_invalid_str_mv |
open access http://purl.org/coar/access_right/c_abf2 Attribution-NonCommercial-NoDerivatives 4.0 International http://creativecommons.org/licenses/by-nc-nd/4.0/ |
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openAccess |
| dc.format.none.fl_str_mv |
application/pdf |
| dc.publisher.none.fl_str_mv |
John Wiley & Sons |
| publisher.none.fl_str_mv |
John Wiley & Sons |
| dc.source.none.fl_str_mv |
reponame:e_Buah Biblioteca Digital Universidad de Alcalá instname:Universidad de Alcalá (UAH) |
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Universidad de Alcalá (UAH) |
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e_Buah Biblioteca Digital Universidad de Alcalá |
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e_Buah Biblioteca Digital Universidad de Alcalá |
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1869420101140217856 |
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15,300719 |