Substitution, abstraction and addition chemistry of low-coordinate gallium and indium ligand systems

Coombs, Natalie D., Bunn, Natalie R., Kays, Deborah L. ORCID: https://orcid.org/0000-0002-4616-6001, Day, Joanna K., Ooi, Li-Ling and Aldridge, Simon 2006. Substitution, abstraction and addition chemistry of low-coordinate gallium and indium ligand systems. Inorganica Chimica Acta 359 (11) , pp. 3693-3698. 10.1016/j.ica.2006.01.021

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Abstract

Substitution, abstraction and addition processes have been shown to be viable chemistries for the modification of ligand systems featuring heavier group 13 element donor atoms. Thus substitution of the bromide in Cp∗Fe(CO)2In(Br)Mes∗ (1) can be carried out with retention of the Fe–In bond, using 1 equiv. of the aryloxide nucleophile [OC6H4tBu-4]− to give Cp∗Fe(CO)2In(OC6H4tBu-4)Mes∗ (2). Structural and spectroscopic comparisons of 1 and 2 reveal that variation in the steric and/or π donor properties of the indyl ligand substituents have little effect on the nature of the Fe–In bond. Sequential reaction of [Cp∗Fe(CO)2]2GaCl (3) with the halide abstraction agent Na[BArf4] and 4-picoline in dichloromethane proceeds via the known two-coordinate gallium cation [{Cp*Fe(CO)2}2(μ-Ga)]+[BArf4]- (4). The net result is replacement of the gallium bound chloride substituent with a 4-picoline moiety, yielding [{Cp*Fe(CO)2}2(μ-Ga·4 pic)]+[BArf4]- (5) via a two-step abstraction/addition process. 5 represents only the second structurally characterized complex containing a cationic three-coordinate gallium centre, and the first displaying bonds to a transition metal.

Item Type:	Article
Date Type:	Publication
Status:	Published
Schools:	Chemistry
Publisher:	Elsevier
ISSN:	0020-1693
Date of Acceptance:	6 January 2006
Last Modified:	12 Jul 2024 14:00
URI:	https://orca.cardiff.ac.uk/id/eprint/170300

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