Iminoborylene complexes: evaluation of synthetic routes towards BN-allenylidenes and unexpected reactivity towards carbodiimides
The synthetic and reaction chemistries of cationic iminoborylene complexes [LnM[double bond, length as m-dash]B[double bond, length as m-dash]N[double bond, length as m-dash]CR2]+, which feature a unique heterocumulene structure, have been systematically investigated. Precursors of the type CpFe(CO)...
| Main Authors: | , , , , |
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| Format: | Journal Article |
| Language: | English |
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2015
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| Online Access: | https://hdl.handle.net/10356/96190 http://hdl.handle.net/10220/38473 |
| _version_ | 1826121913057935360 |
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| author | Niemeyer, J. Kelly, M. J. Riddlestone, I. M. Vidović, Dragoslav Aldridge, S. |
| author2 | School of Physical and Mathematical Sciences |
| author_facet | School of Physical and Mathematical Sciences Niemeyer, J. Kelly, M. J. Riddlestone, I. M. Vidović, Dragoslav Aldridge, S. |
| author_sort | Niemeyer, J. |
| collection | NTU |
| description | The synthetic and reaction chemistries of cationic iminoborylene complexes [LnM[double bond, length as m-dash]B[double bond, length as m-dash]N[double bond, length as m-dash]CR2]+, which feature a unique heterocumulene structure, have been systematically investigated. Precursors of the type CpFe(CO)2B(Cl)NCAr2 (Ar = p-Tol/Mes, 5c/d) have been generated by B-centred substitution chemistry using CpFe(CO)2BCl2 and suitable lithiated ketimines – a reaction which is found to be highly sensitive to the steric bulk at both the metal fragment and the ketimino group. Carbonyl/phosphine exchange (using PCy3 or PPh3), followed by halide abstraction allows for the generation of the cationic iminoborylenes [CpFe(PR3)(CO)(BNCAr2)]+[BArX4]− (R = Cy, Ar = p-Tol/Mes, 12c/d; R = Ph, Ar = Mes, 13d; ArX = 3,5-X2C6H3 where X = Cl, CF3) which have been characterized spectroscopically and by X-ray crystallography. The reactivity of these iminoborylene systems towards a range of nucleophiles and unsaturated substrates has been investigated. The latter includes the first examples of M[double bond, length as m-dash]B metathesis reactivity with a carbodiimide, and results in Fe[double bond, length as m-dash]B cleavage and formation of the isonitrile complexes [CpFe(PCy3)(CO)(CNR)]+[BArCl4]− (R = iPr/Cy, 16/17). |
| first_indexed | 2024-10-01T05:39:55Z |
| format | Journal Article |
| id | ntu-10356/96190 |
| institution | Nanyang Technological University |
| language | English |
| last_indexed | 2024-10-01T05:39:55Z |
| publishDate | 2015 |
| record_format | dspace |
| spelling | ntu-10356/961902023-02-28T19:36:39Z Iminoborylene complexes: evaluation of synthetic routes towards BN-allenylidenes and unexpected reactivity towards carbodiimides Niemeyer, J. Kelly, M. J. Riddlestone, I. M. Vidović, Dragoslav Aldridge, S. School of Physical and Mathematical Sciences DRNTU::Science::Chemistry::Organic chemistry::Carbanions The synthetic and reaction chemistries of cationic iminoborylene complexes [LnM[double bond, length as m-dash]B[double bond, length as m-dash]N[double bond, length as m-dash]CR2]+, which feature a unique heterocumulene structure, have been systematically investigated. Precursors of the type CpFe(CO)2B(Cl)NCAr2 (Ar = p-Tol/Mes, 5c/d) have been generated by B-centred substitution chemistry using CpFe(CO)2BCl2 and suitable lithiated ketimines – a reaction which is found to be highly sensitive to the steric bulk at both the metal fragment and the ketimino group. Carbonyl/phosphine exchange (using PCy3 or PPh3), followed by halide abstraction allows for the generation of the cationic iminoborylenes [CpFe(PR3)(CO)(BNCAr2)]+[BArX4]− (R = Cy, Ar = p-Tol/Mes, 12c/d; R = Ph, Ar = Mes, 13d; ArX = 3,5-X2C6H3 where X = Cl, CF3) which have been characterized spectroscopically and by X-ray crystallography. The reactivity of these iminoborylene systems towards a range of nucleophiles and unsaturated substrates has been investigated. The latter includes the first examples of M[double bond, length as m-dash]B metathesis reactivity with a carbodiimide, and results in Fe[double bond, length as m-dash]B cleavage and formation of the isonitrile complexes [CpFe(PCy3)(CO)(CNR)]+[BArCl4]− (R = iPr/Cy, 16/17). Published version 2015-08-19T08:49:29Z 2019-12-06T19:26:46Z 2015-08-19T08:49:29Z 2019-12-06T19:26:46Z 2015 2015 Journal Article Niemeyer, J., Kelly, M. J., Riddlestone, I. M., Vidovic, D., & Aldridge, S. (2015). Iminoborylene complexes: evaluation of synthetic routes towards BN-allenylidenes and unexpected reactivity towards carbodiimides. Dalton Trans., 44(25), 11294-11305. 1477-9226 https://hdl.handle.net/10356/96190 http://hdl.handle.net/10220/38473 10.1039/C5DT00131E en Dalton Trans. © 2015 The Royal Society of Chemistry. This article is licensed under a Creative Commons Attribution 3.0 Unported Licence. 13 p. application/pdf |
| spellingShingle | DRNTU::Science::Chemistry::Organic chemistry::Carbanions Niemeyer, J. Kelly, M. J. Riddlestone, I. M. Vidović, Dragoslav Aldridge, S. Iminoborylene complexes: evaluation of synthetic routes towards BN-allenylidenes and unexpected reactivity towards carbodiimides |
| title | Iminoborylene complexes: evaluation of synthetic routes towards BN-allenylidenes and unexpected reactivity towards carbodiimides |
| title_full | Iminoborylene complexes: evaluation of synthetic routes towards BN-allenylidenes and unexpected reactivity towards carbodiimides |
| title_fullStr | Iminoborylene complexes: evaluation of synthetic routes towards BN-allenylidenes and unexpected reactivity towards carbodiimides |
| title_full_unstemmed | Iminoborylene complexes: evaluation of synthetic routes towards BN-allenylidenes and unexpected reactivity towards carbodiimides |
| title_short | Iminoborylene complexes: evaluation of synthetic routes towards BN-allenylidenes and unexpected reactivity towards carbodiimides |
| title_sort | iminoborylene complexes evaluation of synthetic routes towards bn allenylidenes and unexpected reactivity towards carbodiimides |
| topic | DRNTU::Science::Chemistry::Organic chemistry::Carbanions |
| url | https://hdl.handle.net/10356/96190 http://hdl.handle.net/10220/38473 |
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