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)...
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sg-ntu-dr.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 |
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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 |
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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). |
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School of Physical and Mathematical Sciences |
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School of Physical and Mathematical Sciences Niemeyer, J. Kelly, M. J. Riddlestone, I. M. Vidović, Dragoslav Aldridge, S. |
format |
Article |
author |
Niemeyer, J. Kelly, M. J. Riddlestone, I. M. Vidović, Dragoslav Aldridge, S. |
author_sort |
Niemeyer, J. |
title |
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_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_sort |
iminoborylene complexes: evaluation of synthetic routes towards bn-allenylidenes and unexpected reactivity towards carbodiimides |
publishDate |
2015 |
url |
https://hdl.handle.net/10356/96190 http://hdl.handle.net/10220/38473 |
_version_ |
1759855764123418624 |