exo-closo-rhodacarboranes: synthesis and characterisation of [{exo-(R3P)(2)Rh}(closo-CB11H12)][R3P = P(OMe)(3), PCy3, 1/2dppe]
Addition of H2 to CH2Cl2 solutions of [(diene)Rh(L)2][closo-CB11H12] (diene=norbornadiene, cyclooctadiene, L=PCy3, P(OMe)3, 1/2dppe) results in the formation of the exo-closo complexes [(PR3)2Rh(closo-CB11 H12)]. These have been characterised in solution by 1H- and 11B-NMR spectroscopy, and for L=PC...
| Main Authors: | , , , , , |
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| Format: | Journal article |
| Language: | English |
| Published: |
2003
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| _version_ | 1797054954525949952 |
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| author | Rifat, A Laing, V Kociok-Kohn, G Mahon, M Ruggiero, G Weller, A |
| author_facet | Rifat, A Laing, V Kociok-Kohn, G Mahon, M Ruggiero, G Weller, A |
| author_sort | Rifat, A |
| collection | OXFORD |
| description | Addition of H2 to CH2Cl2 solutions of [(diene)Rh(L)2][closo-CB11H12] (diene=norbornadiene, cyclooctadiene, L=PCy3, P(OMe)3, 1/2dppe) results in the formation of the exo-closo complexes [(PR3)2Rh(closo-CB11 H12)]. These have been characterised in solution by 1H- and 11B-NMR spectroscopy, and for L=PCy3 by a single crystal X-ray diffraction study. This suggests that the metal fragment is bound with the cage through the 7,8- and not the 7,12-{BH} vertices. DFT calculations on a model system where L=PMe3 show that there is only a negligible energy difference between these two isomers (1 kcal mol-1), suggesting that both represent stable structures. The salient spectroscopic markers that indicate an interaction of [closo-CB11 H12]- with a metal fragment are discussed and compared across a range of metal complexes. Large upfield shifts in the 11B-NMR spectrum and a small downfield shift of the CH vertex in the 1H-NMR spectrum are shown to the most reliable indicators of borane interaction in solution. © 2003 Elsevier Science B.V. All rights reserved. |
| first_indexed | 2024-03-06T19:04:36Z |
| format | Journal article |
| id | oxford-uuid:14b27b61-f618-4547-acb4-dec5f3307098 |
| institution | University of Oxford |
| language | English |
| last_indexed | 2024-03-06T19:04:36Z |
| publishDate | 2003 |
| record_format | dspace |
| spelling | oxford-uuid:14b27b61-f618-4547-acb4-dec5f33070982022-03-26T10:21:14Zexo-closo-rhodacarboranes: synthesis and characterisation of [{exo-(R3P)(2)Rh}(closo-CB11H12)][R3P = P(OMe)(3), PCy3, 1/2dppe]Journal articlehttp://purl.org/coar/resource_type/c_dcae04bcuuid:14b27b61-f618-4547-acb4-dec5f3307098EnglishSymplectic Elements at Oxford2003Rifat, ALaing, VKociok-Kohn, GMahon, MRuggiero, GWeller, AAddition of H2 to CH2Cl2 solutions of [(diene)Rh(L)2][closo-CB11H12] (diene=norbornadiene, cyclooctadiene, L=PCy3, P(OMe)3, 1/2dppe) results in the formation of the exo-closo complexes [(PR3)2Rh(closo-CB11 H12)]. These have been characterised in solution by 1H- and 11B-NMR spectroscopy, and for L=PCy3 by a single crystal X-ray diffraction study. This suggests that the metal fragment is bound with the cage through the 7,8- and not the 7,12-{BH} vertices. DFT calculations on a model system where L=PMe3 show that there is only a negligible energy difference between these two isomers (1 kcal mol-1), suggesting that both represent stable structures. The salient spectroscopic markers that indicate an interaction of [closo-CB11 H12]- with a metal fragment are discussed and compared across a range of metal complexes. Large upfield shifts in the 11B-NMR spectrum and a small downfield shift of the CH vertex in the 1H-NMR spectrum are shown to the most reliable indicators of borane interaction in solution. © 2003 Elsevier Science B.V. All rights reserved. |
| spellingShingle | Rifat, A Laing, V Kociok-Kohn, G Mahon, M Ruggiero, G Weller, A exo-closo-rhodacarboranes: synthesis and characterisation of [{exo-(R3P)(2)Rh}(closo-CB11H12)][R3P = P(OMe)(3), PCy3, 1/2dppe] |
| title | exo-closo-rhodacarboranes: synthesis and characterisation of [{exo-(R3P)(2)Rh}(closo-CB11H12)][R3P = P(OMe)(3), PCy3, 1/2dppe] |
| title_full | exo-closo-rhodacarboranes: synthesis and characterisation of [{exo-(R3P)(2)Rh}(closo-CB11H12)][R3P = P(OMe)(3), PCy3, 1/2dppe] |
| title_fullStr | exo-closo-rhodacarboranes: synthesis and characterisation of [{exo-(R3P)(2)Rh}(closo-CB11H12)][R3P = P(OMe)(3), PCy3, 1/2dppe] |
| title_full_unstemmed | exo-closo-rhodacarboranes: synthesis and characterisation of [{exo-(R3P)(2)Rh}(closo-CB11H12)][R3P = P(OMe)(3), PCy3, 1/2dppe] |
| title_short | exo-closo-rhodacarboranes: synthesis and characterisation of [{exo-(R3P)(2)Rh}(closo-CB11H12)][R3P = P(OMe)(3), PCy3, 1/2dppe] |
| title_sort | exo closo rhodacarboranes synthesis and characterisation of exo r3p 2 rh closo cb11h12 r3p p ome 3 pcy3 1 2dppe |
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