Schmidt, Monika and Seitz, Andreas E. and Eckhardt, Maria and Balazs, Gabor and Peresypkina, Eugenia V. and Virovets, Alexander V. and Riedlberger, Felix and Bodensteiner, Michael and Zolnhofer, Eva M. and Meyer, Karsten and Scheer, Manfred (2017) Transfer Reagent for Bonding Isomers of Iron Complexes. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 139 (40). pp. 13981-13984. ISSN 0002-7863,
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The cothermolysis of As-4 and [Cp"Zr-2-(CO)(2)] (Cp" = eta(5)-C(5)H(3)tBu(2)) results in the formation of [Cp"Zr-2(eta(1:1)-As-4)] (1) in high yields and the arsenic-rich complex [(Cp"Zr-2)(Cp"Zr)(mu,eta(2:2:1)-As-5)] (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(mu-Br)](2) (Cp"' = eta(5)-C(5)H(2)tBu(3)) yields the unprecedented bond isomeric complexes [(Cp"' Fe)(2)(mu,eta(4:4)-As-4)] (3a) and [(Cp"' Fe)(2)(mu,eta(4:4)-cycio-As-4)] (3b). In contrast, the analogous reaction with the Cp-Bn derivative [(CpFe)-Fe-Bn(mu-Br)](2) (Cp-Bn = eta(5)-C-5(CH2(C6H5)(5)) leads exclusively to the triple decker complex [((CpFe)-Fe-Bn)(2)(mu,eta(4:4)-As-4] (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 [((CpFe)-Fe-Bn)(2)(mu,eta(5:5)-As-5)][BF4] (5), which is a product expanded by one arsenic atom, instead of the expected complex [((CpFe)-Fe-Bn)(2)(mu,eta(4:4)-cyclo-As-4](+).
| Item Type: | Article |
|---|---|
| Uncontrolled Keywords: | TRANSITION-METAL-COMPLEXES; P-4 ACTIVATION; ELECTRON-DIFFRACTION; ZIRCONIUM COMPLEXES; LIGAND COMPLEXES; PHOSPHORUS; AS-4; ELEMENTS; REACTIVITY; DISILENES; |
| Subjects: | 500 Science > 540 Chemistry & allied sciences |
| Divisions: | Chemistry and Pharmacy > Institut für Anorganische Chemie > Chair Prof. Dr. Manfred Scheer |
| Depositing User: | Dr. Gernot Deinzer |
| Date Deposited: | 14 Dec 2018 13:19 |
| Last Modified: | 20 Feb 2019 10:53 |
| URI: | https://pred.uni-regensburg.de/id/eprint/2010 |
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