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
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(η1:1-As4)] (1) in high yields and the arsenic-rich complex [(Cp″2Zr)(Cp″Zr)(μ, η2:2:1-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, η4:4-As4)] (3a) and [(Cp'Fe)2(μ, η4:4-cyclo-As4)] (3b). In contrast, the analogous reaction with the CpBn derivative [CpBnFe(μ-Br)]2 (CpBn = η5-C5(CH2(C6H5)5) leads exclusively to the triple decker complex [(CpBnFe)2(μ, η4:4-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 [(CpBnFe)2(μ, η5:5-As5)][BF4] (5), which is a product expanded by one arsenic atom, instead of the expected complex [(CpBnFe)2(μ, η4:4-cyclo-As4)]+.
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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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