Transfer Reagent for Bonding Isomers of Iron Complexes

Schmidt M, Seitz AE, Eckhardt M, Balazs G, Peresypkina EV, Virovets AV, Riedlberger F, Bodensteiner M, Zolnhofer E, Meyer K, Scheer M (2017)

Publication Type: Journal article

Publication year: 2017

Journal

Journal of the American Chemical Society American Chemical Society

Book Volume: 139

Pages Range: 13981-13984

Journal Issue: 40

DOI: 10.1021/jacs.7b07354

Abstract

The cothermolysis of As4 and [Cp″2Zr(CO)2] (Cp″ = η⁵-C5H3tBu2) results in the formation of [Cp″2Zr(η^1:1-As4)] (1) in high yields and the arsenic-rich complex [(Cp″2Zr)(Cp″Zr)(μ, η^2:2:1-As5)] (2) as a minor product. In contrast to yellow arsenic, 1 is a light-stable, weighable and storable arsenic source for subsequent reactions. The transfer reaction of 1 with [Cp'Fe(μ-Br)]2 (Cp' = η⁵-C5H2tBu3) yields the unprecedented bond isomeric complexes [(Cp'Fe)2(μ, η^4:4-As4)] (3a) and [(Cp'Fe)2(μ, η^4:4-cyclo-As4)] (3b). In contrast, the analogous reaction with the Cp^Bn derivative [Cp^BnFe(μ-Br)]2 (Cp^Bn = η⁵-C5(CH2(C6H5)5) leads exclusively to the triple decker complex [(Cp^BnFe)2(μ, η^4:4-As4)] (4) possessing the tetraarsabutadiene-type ligand analogous to 3a. To elucidate the stability of the bonding isomers 3a and 3b, DFT calculations were performed. The oxidation of 4 with AgBF4 affords [(Cp^BnFe)2(μ, η^5:5-As5)][BF4] (5), which is a product expanded by one arsenic atom, instead of the expected complex [(Cp^BnFe)2(μ, η^4:4-cyclo-As4)]⁺.

Authors with CRIS profile

Eva Zolnhofer Lehrstuhl für Anorganische und Allgemeine Chemie Karsten Meyer Lehrstuhl für Anorganische und Allgemeine Chemie

Involved external institutions

Universität Regensburg

Germany (DE)

How to cite

APA:

Schmidt, M., Seitz, A.E., Eckhardt, M., Balazs, G., Peresypkina, E.V., Virovets, A.V.,... Scheer, M. (2017). Transfer Reagent for Bonding Isomers of Iron Complexes. Journal of the American Chemical Society, 139(40), 13981-13984. https://doi.org/10.1021/jacs.7b07354

MLA:

Schmidt, Monika, et al. "Transfer Reagent for Bonding Isomers of Iron Complexes." Journal of the American Chemical Society 139.40 (2017): 13981-13984.

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