Tuning coordination in s-block carbazol-9-yl complexes
1,3,6,8-Tetra-tert-butylcarbazol-9-yl and 1,8-diaryl-3,6-di(tert-butyl)carbazol-9-yl ligands have been utilized in the synthesis of potassium and magnesium complexes. The potassium complexes (1,3,6,8-tBu4carb)K(THF)4 (1; carb=C12H4N), [(1,8-Xyl2-3,6-tBu2carb)K(THF)]2 (2; Xyl=3,5-Me2C6H3) and (1,8-Me...
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Wiley-VCH Verlag
2015
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| Online Access: | https://eprints.nottingham.ac.uk/30567/ |
| _version_ | 1848794012724494336 |
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| author | Ortu, Fabrizio Moxey, Graeme J. Blake, Alexander J. Lewis, William Kays, Deborah L. |
| author_facet | Ortu, Fabrizio Moxey, Graeme J. Blake, Alexander J. Lewis, William Kays, Deborah L. |
| author_sort | Ortu, Fabrizio |
| building | Nottingham Research Data Repository |
| collection | Online Access |
| description | 1,3,6,8-Tetra-tert-butylcarbazol-9-yl and 1,8-diaryl-3,6-di(tert-butyl)carbazol-9-yl ligands have been utilized in the synthesis of potassium and magnesium complexes. The potassium complexes (1,3,6,8-tBu4carb)K(THF)4 (1; carb=C12H4N), [(1,8-Xyl2-3,6-tBu2carb)K(THF)]2 (2; Xyl=3,5-Me2C6H3) and (1,8-Mes2-3,6-tBu2carb)K(THF)2 (3; Mes=2,4,6-Me3C6H2) were reacted with MgI2 to give the Hauser bases 1,3,6,8-tBu4carbMgI(THF)2 (4) and 1,8-Ar2-3,6-tBu2carbMgI(THF) (Ar=Xyl 5, Ar=Mes 6). Structural investigations of the potassium and magnesium derivatives highlight significant differences in the coordination motifs, which depend on the nature of the 1- and 8-substituents: 1,8-di(tert-butyl)-substituted ligands gave π-type compounds (1 and 4), in which the carbazolyl ligand acts as a multi-hapto donor, with the metal cations positioned below the coordination plane in a half-sandwich conformation, whereas the use of 1,8-diaryl substituted ligands gave σ-type complexes (2 and 6). Space-filling diagrams and percent buried volume calculations indicated that aryl-substituted carbazolyl ligands offer a steric cleft better suited to stabilization of low-coordinate magnesium complexes. |
| first_indexed | 2025-11-14T19:09:26Z |
| format | Article |
| id | nottingham-30567 |
| institution | University of Nottingham Malaysia Campus |
| institution_category | Local University |
| last_indexed | 2025-11-14T19:09:26Z |
| publishDate | 2015 |
| publisher | Wiley-VCH Verlag |
| recordtype | eprints |
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| spelling | nottingham-305672020-05-04T17:04:40Z https://eprints.nottingham.ac.uk/30567/ Tuning coordination in s-block carbazol-9-yl complexes Ortu, Fabrizio Moxey, Graeme J. Blake, Alexander J. Lewis, William Kays, Deborah L. 1,3,6,8-Tetra-tert-butylcarbazol-9-yl and 1,8-diaryl-3,6-di(tert-butyl)carbazol-9-yl ligands have been utilized in the synthesis of potassium and magnesium complexes. The potassium complexes (1,3,6,8-tBu4carb)K(THF)4 (1; carb=C12H4N), [(1,8-Xyl2-3,6-tBu2carb)K(THF)]2 (2; Xyl=3,5-Me2C6H3) and (1,8-Mes2-3,6-tBu2carb)K(THF)2 (3; Mes=2,4,6-Me3C6H2) were reacted with MgI2 to give the Hauser bases 1,3,6,8-tBu4carbMgI(THF)2 (4) and 1,8-Ar2-3,6-tBu2carbMgI(THF) (Ar=Xyl 5, Ar=Mes 6). Structural investigations of the potassium and magnesium derivatives highlight significant differences in the coordination motifs, which depend on the nature of the 1- and 8-substituents: 1,8-di(tert-butyl)-substituted ligands gave π-type compounds (1 and 4), in which the carbazolyl ligand acts as a multi-hapto donor, with the metal cations positioned below the coordination plane in a half-sandwich conformation, whereas the use of 1,8-diaryl substituted ligands gave σ-type complexes (2 and 6). Space-filling diagrams and percent buried volume calculations indicated that aryl-substituted carbazolyl ligands offer a steric cleft better suited to stabilization of low-coordinate magnesium complexes. Wiley-VCH Verlag 2015-03-15 Article PeerReviewed Ortu, Fabrizio, Moxey, Graeme J., Blake, Alexander J., Lewis, William and Kays, Deborah L. (2015) Tuning coordination in s-block carbazol-9-yl complexes. Chemistry - a European Journal, 21 (18). pp. 6949-6956. ISSN 0947-6539 http://onlinelibrary.wiley.com/doi/10.1002/chem.201406490/abstract doi:10.1002/chem.201406490 doi:10.1002/chem.201406490 |
| spellingShingle | Ortu, Fabrizio Moxey, Graeme J. Blake, Alexander J. Lewis, William Kays, Deborah L. Tuning coordination in s-block carbazol-9-yl complexes |
| title | Tuning coordination in s-block carbazol-9-yl complexes |
| title_full | Tuning coordination in s-block carbazol-9-yl complexes |
| title_fullStr | Tuning coordination in s-block carbazol-9-yl complexes |
| title_full_unstemmed | Tuning coordination in s-block carbazol-9-yl complexes |
| title_short | Tuning coordination in s-block carbazol-9-yl complexes |
| title_sort | tuning coordination in s-block carbazol-9-yl complexes |
| url | https://eprints.nottingham.ac.uk/30567/ https://eprints.nottingham.ac.uk/30567/ https://eprints.nottingham.ac.uk/30567/ |