Kays, Deborah L.  ORCID: https://orcid.org/0000-0002-4616-6001, Rossin, Andrea ORCID: https://orcid.org/0000-0002-1283-2803, Day, Joanne K., Ooi, Li-Ling and Aldridge, Simon
2005.
Synthetic and reaction chemistry of heteroatom stabilized boryl and cationic borylene complexes.
Dalton Transactions
(2)
, pp. 399-410.
10.1039/B512275A
|
Abstract
The synthesis, spectroscopic and structural characterization of the aryloxy and amino functionalized chloroboryl complexes (η5-C5R5)Fe(CO)2B(OMes)Cl (R = H, 2a; R = Me, 3a) and (η5-C5H5)Fe(CO)2B(NiPr2)Cl (7a) are reported. Compound 2a is shown to be a versatile substrate for further boron-centred substitution chemistry leading to the asymmetric boryl complexes (η5-C5H5)Fe(CO)2B(OMes)ERn [ERn = OC6H4tBu-4, 2c; ERn = SPh, 2d] with retention of the metal–boron bond. The reactivities of 2a, 3a and 7a towards the halide abstraction agent Na[BArf4] have also been examined, in order to investigate the potential for the generation of cationic heteroatom-stabilized terminal borylene complexes. The application of this methodology to the mesityloxy derivatives 2a and 3a gives rise to B–F containing products, presumably via fluoride abstraction from the [BArf4]− counter-ion. By contrast, amino-functionalized complex 7a is more amenable to this approach, and the thermally robust terminal aminoborylene complex [(η5-C5H5)Fe(CO)2B(NiPr2)][BArf4] (9) can be isolated in ca. 50% yield. The reactivity of 9 towards a range of nucleophilic and/or unsaturated reagents has been examined, with examples of addition, protonolysis and metathesis chemistries having been established.
| Item Type: | Article |
|---|---|
| Date Type: | Publication |
| Status: | Published |
| Schools: | Chemistry |
| Publisher: | Royal Society of Chemistry |
| ISSN: | 1477-9226 |
| Date of Acceptance: | 17 October 2005 |
| Last Modified: | 05 Jul 2024 11:15 |
| URI: | https://orca.cardiff.ac.uk/id/eprint/170316 |
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