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Towards Weakly Coordinating Anions with the Extremely Electron Withdrawing Perfluoropyridinoxy Ligand –OC5F4N

Riddlestone, Ian M., Keller, S., Kirschenmann, F., Schorpp, M. and Krossing, I. (2019) Towards Weakly Coordinating Anions with the Extremely Electron Withdrawing Perfluoropyridinoxy Ligand –OC5F4N European Journal of Inorganic Chemistry, 2019 (1). pp. 59-67.

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The extreme electron withdrawing properties of the perfluoropyridinoxy ligand –OC5F4N were used for the preparation of new (weakly) coordinating borate and aluminate anions of the type [E(OC5F4N)4]– (E = B or Al). These new anions are based on the potent parent Lewis acids E(OC5F4N)3, which possess exceptionally high calculated fluoride ion affinities (FIAs) of 500 and 587 kJ mol–1 for E = B and Al respectively. For aluminum, this extreme Lewis acidity dominates the chemistry and from mixtures of the neutral polymeric Lewis acid [Al(OC5F4N)3]n, the five‐ and six‐coordinate complexes Al(OC5F4N)3(OEt2)2 (1) and [Al(OC5F4N)2(µ‐OC5F4N) (NCMe)2]2 (2) were crystallized upon addition of ether or MeCN. The aluminate salts M[Al(OC5F4N)4] (M = Li or K) were prepared from the reaction between the alcohol 4‐HO–C5F4N and either LiAlH4 or K[AlEt4] respectively. The aluminate anion [Al(OC5F4N)4]– remains Lewis acidic coordinating small donor molecules forming [Al(OC5F4N)4(L)]– (L = THF or NMe3) and even supports formation and structural characterisation of the aluminum dianion containing salt [Na(OEt2)2][Na][Al(OC5F4N)5] (8). The from NaBH4 and 4‐HO–C5F4N accessible borate salt Na[B(OC5F4N)4] shows increased kinetic stability in comparison to the aluminum analogue.

Item Type: Article
Divisions : Faculty of Engineering and Physical Sciences > Chemistry
Authors :
Riddlestone, Ian
Keller, S.
Kirschenmann, F.
Schorpp, M.
Krossing, I.
Date : 3 January 2019
DOI : 10.1002/ejic.201801136
Uncontrolled Keywords : Aluminum, Anions, Borates, Lewis acids, Weakly coordinating anions
Depositing User : Clive Harris
Date Deposited : 19 Jun 2019 14:51
Last Modified : 19 Jun 2019 14:59

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