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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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Autores principales: Moggach, Stephen A., Skelton, Brian W., Foster, Daven J.
Formato: Online Artículo Texto
Lenguaje:English
Publicado: International Union of Crystallography 2020
Materias:
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.
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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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