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Crystal structures of [μ(2)-(R(a),S(a),3aR,7aR)-1,3-bis(2,7-dicyclohexylnaphthalen-1-yl)octahydro-1H-benzo[d]imidazolidin-2-ylidene]chlorido(η(4)-1,5-cyclooctadiene)iridium dichloromethane monosolvate and [μ(2)-(S(a),S(a),3aR,7aR)-1,3-bis(2,7-dicyclohexylnaphthalen-1-yl)octahydro-1H-benzo[d]imidazolidin-2-ylidene]chlorido(η(4)-1,5-cyclooctadiene)iridium
The title compounds, [Ir(C(51)H(64)N(2))Cl(C(8)H(12))]·CH(2)Cl(2), (I), and [Ir(C(51)H(64)N(2))Cl(C(8)H(12))], (II), represent the first two examples of hexahydrobenzoimidazole-based N-heterocyclic carbene (NHC) iridium complexes. The diastereomeric complexes differing only in their axial chirali...
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Formato: | Online Artículo Texto |
Lenguaje: | English |
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International Union of Crystallography
2020
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Acceso en línea: | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC7534235/ https://www.ncbi.nlm.nih.gov/pubmed/33117560 http://dx.doi.org/10.1107/S2056989020011603 |
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author | Moggach, Stephen A. Skelton, Brian W. Foster, Daven J. |
author_facet | Moggach, Stephen A. Skelton, Brian W. Foster, Daven J. |
author_sort | Moggach, Stephen A. |
collection | PubMed |
description | The title compounds, [Ir(C(51)H(64)N(2))Cl(C(8)H(12))]·CH(2)Cl(2), (I), and [Ir(C(51)H(64)N(2))Cl(C(8)H(12))], (II), represent the first two examples of hexahydrobenzoimidazole-based N-heterocyclic carbene (NHC) iridium complexes. The diastereomeric complexes differing only in their axial chirality, which could be separated via column chromatography, show noticeable differences in their (1)H NMR spectra. Compound (I) crystallizes in the monoclinic system (P2(1)) with two independent complexes and two half-occupied dichloromethane molecules in the asymmetric unit, while compound (II) crystallizes in the orthorhombic system (P2(1)2(1)2(1)) with one complex in the asymmetric unit. The fused five-membered N-heterocycles of NHCs show unusually high backbone torsion angles of −34.1 (5) and −30.9 (5)° for (I) and −31.5 (7)° for (II), but the Ir—C(carbene) bond lengths of 2.046 (6) and 2.021 (6) Å for (I) and 2.045 (8) Å for (II) present typical NHC—Ir bond lengths. The solvent molecule in the crystal of (I) was found to be highly disordered and its contribution to the scattering was masked using the solvent-masking routine smtbx.mask in OLEX2 [Dolomanov et al. (2009 ▸). J. Appl. Cryst. 42, 339–341]. The solvent contribution is not included in the reported chemical formula and other crystal data. |
format | Online Article Text |
id | pubmed-7534235 |
institution | National Center for Biotechnology Information |
language | English |
publishDate | 2020 |
publisher | International Union of Crystallography |
record_format | MEDLINE/PubMed |
spelling | pubmed-75342352020-10-27 Crystal structures of [μ(2)-(R(a),S(a),3aR,7aR)-1,3-bis(2,7-dicyclohexylnaphthalen-1-yl)octahydro-1H-benzo[d]imidazolidin-2-ylidene]chlorido(η(4)-1,5-cyclooctadiene)iridium dichloromethane monosolvate and [μ(2)-(S(a),S(a),3aR,7aR)-1,3-bis(2,7-dicyclohexylnaphthalen-1-yl)octahydro-1H-benzo[d]imidazolidin-2-ylidene]chlorido(η(4)-1,5-cyclooctadiene)iridium Moggach, Stephen A. Skelton, Brian W. Foster, Daven J. Acta Crystallogr E Crystallogr Commun Research Communications The title compounds, [Ir(C(51)H(64)N(2))Cl(C(8)H(12))]·CH(2)Cl(2), (I), and [Ir(C(51)H(64)N(2))Cl(C(8)H(12))], (II), represent the first two examples of hexahydrobenzoimidazole-based N-heterocyclic carbene (NHC) iridium complexes. The diastereomeric complexes differing only in their axial chirality, which could be separated via column chromatography, show noticeable differences in their (1)H NMR spectra. Compound (I) crystallizes in the monoclinic system (P2(1)) with two independent complexes and two half-occupied dichloromethane molecules in the asymmetric unit, while compound (II) crystallizes in the orthorhombic system (P2(1)2(1)2(1)) with one complex in the asymmetric unit. The fused five-membered N-heterocycles of NHCs show unusually high backbone torsion angles of −34.1 (5) and −30.9 (5)° for (I) and −31.5 (7)° for (II), but the Ir—C(carbene) bond lengths of 2.046 (6) and 2.021 (6) Å for (I) and 2.045 (8) Å for (II) present typical NHC—Ir bond lengths. The solvent molecule in the crystal of (I) was found to be highly disordered and its contribution to the scattering was masked using the solvent-masking routine smtbx.mask in OLEX2 [Dolomanov et al. (2009 ▸). J. Appl. Cryst. 42, 339–341]. The solvent contribution is not included in the reported chemical formula and other crystal data. International Union of Crystallography 2020-09-04 /pmc/articles/PMC7534235/ /pubmed/33117560 http://dx.doi.org/10.1107/S2056989020011603 Text en © Moggach et al. 2020 http://creativecommons.org/licenses/by/4.0/ This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.http://creativecommons.org/licenses/by/4.0/ |
spellingShingle | Research Communications Moggach, Stephen A. Skelton, Brian W. Foster, Daven J. Crystal structures of [μ(2)-(R(a),S(a),3aR,7aR)-1,3-bis(2,7-dicyclohexylnaphthalen-1-yl)octahydro-1H-benzo[d]imidazolidin-2-ylidene]chlorido(η(4)-1,5-cyclooctadiene)iridium dichloromethane monosolvate and [μ(2)-(S(a),S(a),3aR,7aR)-1,3-bis(2,7-dicyclohexylnaphthalen-1-yl)octahydro-1H-benzo[d]imidazolidin-2-ylidene]chlorido(η(4)-1,5-cyclooctadiene)iridium |
title | Crystal structures of [μ(2)-(R(a),S(a),3aR,7aR)-1,3-bis(2,7-dicyclohexylnaphthalen-1-yl)octahydro-1H-benzo[d]imidazolidin-2-ylidene]chlorido(η(4)-1,5-cyclooctadiene)iridium dichloromethane monosolvate and [μ(2)-(S(a),S(a),3aR,7aR)-1,3-bis(2,7-dicyclohexylnaphthalen-1-yl)octahydro-1H-benzo[d]imidazolidin-2-ylidene]chlorido(η(4)-1,5-cyclooctadiene)iridium |
title_full | Crystal structures of [μ(2)-(R(a),S(a),3aR,7aR)-1,3-bis(2,7-dicyclohexylnaphthalen-1-yl)octahydro-1H-benzo[d]imidazolidin-2-ylidene]chlorido(η(4)-1,5-cyclooctadiene)iridium dichloromethane monosolvate and [μ(2)-(S(a),S(a),3aR,7aR)-1,3-bis(2,7-dicyclohexylnaphthalen-1-yl)octahydro-1H-benzo[d]imidazolidin-2-ylidene]chlorido(η(4)-1,5-cyclooctadiene)iridium |
title_fullStr | Crystal structures of [μ(2)-(R(a),S(a),3aR,7aR)-1,3-bis(2,7-dicyclohexylnaphthalen-1-yl)octahydro-1H-benzo[d]imidazolidin-2-ylidene]chlorido(η(4)-1,5-cyclooctadiene)iridium dichloromethane monosolvate and [μ(2)-(S(a),S(a),3aR,7aR)-1,3-bis(2,7-dicyclohexylnaphthalen-1-yl)octahydro-1H-benzo[d]imidazolidin-2-ylidene]chlorido(η(4)-1,5-cyclooctadiene)iridium |
title_full_unstemmed | Crystal structures of [μ(2)-(R(a),S(a),3aR,7aR)-1,3-bis(2,7-dicyclohexylnaphthalen-1-yl)octahydro-1H-benzo[d]imidazolidin-2-ylidene]chlorido(η(4)-1,5-cyclooctadiene)iridium dichloromethane monosolvate and [μ(2)-(S(a),S(a),3aR,7aR)-1,3-bis(2,7-dicyclohexylnaphthalen-1-yl)octahydro-1H-benzo[d]imidazolidin-2-ylidene]chlorido(η(4)-1,5-cyclooctadiene)iridium |
title_short | Crystal structures of [μ(2)-(R(a),S(a),3aR,7aR)-1,3-bis(2,7-dicyclohexylnaphthalen-1-yl)octahydro-1H-benzo[d]imidazolidin-2-ylidene]chlorido(η(4)-1,5-cyclooctadiene)iridium dichloromethane monosolvate and [μ(2)-(S(a),S(a),3aR,7aR)-1,3-bis(2,7-dicyclohexylnaphthalen-1-yl)octahydro-1H-benzo[d]imidazolidin-2-ylidene]chlorido(η(4)-1,5-cyclooctadiene)iridium |
title_sort | crystal structures of [μ(2)-(r(a),s(a),3ar,7ar)-1,3-bis(2,7-dicyclohexylnaphthalen-1-yl)octahydro-1h-benzo[d]imidazolidin-2-ylidene]chlorido(η(4)-1,5-cyclooctadiene)iridium dichloromethane monosolvate and [μ(2)-(s(a),s(a),3ar,7ar)-1,3-bis(2,7-dicyclohexylnaphthalen-1-yl)octahydro-1h-benzo[d]imidazolidin-2-ylidene]chlorido(η(4)-1,5-cyclooctadiene)iridium |
topic | Research Communications |
url | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC7534235/ https://www.ncbi.nlm.nih.gov/pubmed/33117560 http://dx.doi.org/10.1107/S2056989020011603 |
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