Fe=B double bonds: Synthetic, structural, and reaction chemistry of cationic terminal borylene complexes

Coombs, Deborah L. ORCID: https://orcid.org/0000-0002-4616-6001, Aldridge, Simon, Rossin, Andrea, Jones, Cameron and Willock, David J. ORCID: https://orcid.org/0000-0002-8893-1090 2004. Fe=B double bonds: Synthetic, structural, and reaction chemistry of cationic terminal borylene complexes. Organometallics 23 (12) , pp. 2911-2926. 10.1021/om049793e

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Abstract

Application of halide abstraction chemistry to asymmetric haloboryl complexes (η5-C5Me5)Fe(CO)2B(ERn)X leads to the first synthetic route to cationic multiply bonded group 13 diyl species, [(η5-C5Me5)Fe(CO)2B(ERn)]+. The roles of steric bulk and π electron release within the ERn substituent in generating tractable borylene complexes have been probed, as has the nature of the counterion. A combination of spectroscopic, structural, and computational techniques leads to the conclusion that the bonding in complexes such as [(η5-C5Me5)Fe(CO)2B(Mes)]+ is best described as an FeB double bond composed of B→Fe σ donor and Fe→B π back-bonding components. An extended study of the fundamental reactivity of cationic borylene systems reveals that this is dominated not only by nucleophilic addition at boron but also by iron-centered substitution chemistry leading to overall displacement of the borylene ligand.

Item Type:	Article
Date Type:	Publication
Status:	Published
Schools:	Chemistry
Publisher:	American Chemical Society
ISSN:	0276-7333
Last Modified:	12 Jul 2024 14:59
URI:	https://orca.cardiff.ac.uk/id/eprint/170535

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