Cyaarside (CAs-) and 1,3-Diarsaallendiide (AsCAs2-) Ligands Coordinated to Uranium and Generated via Activation of the Arsaethynolate Ligand (OCAs-)

Hörger C, Heinemann FW, Louyriac E, Rigo M, Maron L, Grutzmacher H, Driess M, Meyer K (2019)

Publication Type: Journal article

Publication year: 2019

Journal

Angewandte Chemie International Edition Wiley

Book Volume: 58

Pages Range: 1679-1683

Journal Issue: 6

DOI: 10.1002/anie.201811332

Abstract

Reaction of the trivalent uranium complex [(((ArO)-Ar-Ad,Me)(3)N)U(DME)] with one molar equiv [Na(OCAs)(dioxane)(3)], in the presence of 2.2.2-crypt, yields [Na(2.2.2-crypt)][{(((ArO)-Ar-Ad,Me)(3)N)U-IV(THF)}(-O){(((ArO)-Ar-Ad,Me)(3)N)U-IV(CAs)}] (1), the first example of a coordinated (1)-cyaarside ligand (CAs-). Formation of the terminal CAs- is promoted by the highly reducing, oxophilic U-III precursor [(((ArO)-Ar-Ad,Me)(3)N)U(DME)] and proceeds through reductive C-O bond cleavage of the bound arsaethynolate anion, OCAs-. If two equiv of OCAs- react with the U-III precursor, the binuclear, -oxo-bridged U-2(IV/IV) complex [Na(2.2.2-crypt)](2)[{(((ArO)-Ar-Ad,Me)(3)N)U-IV}(2)(-O)(-AsCAs)] (2), comprising the hitherto unknown :(1),(1)-coordinated (AsCAs)(2-) ligand, is isolated. The mechanistic pathway to 2 involves the decarbonylation of a dimeric intermediate formed in the reaction of 1 with OCAs-. An alternative pathway to complex 2 is by conversion of 1 via addition of one further equiv of OCAs-.

Authors with CRIS profile

Christopher Hörger Lehrstuhl für Anorganische und Allgemeine Chemie Frank Wilhelm Heinemann Lehrstuhl für Anorganische und Allgemeine Chemie Karsten Meyer Lehrstuhl für Anorganische und Allgemeine Chemie

Involved external institutions

Université Fédérale de Toulouse Midi-Pyrénées FR France (FR) Technische Universität Berlin DE Germany (DE) École Polytechnique Fédérale de Lausanne (EPFL) CH Switzerland (CH)

How to cite

APA:

Hörger, C., Heinemann, F.W., Louyriac, E., Rigo, M., Maron, L., Grutzmacher, H.,... Meyer, K. (2019). Cyaarside (CAs-) and 1,3-Diarsaallendiide (AsCAs2-) Ligands Coordinated to Uranium and Generated via Activation of the Arsaethynolate Ligand (OCAs-). Angewandte Chemie International Edition, 58(6), 1679-1683. https://dx.doi.org/10.1002/anie.201811332

MLA:

Hörger, Christopher, et al. "Cyaarside (CAs-) and 1,3-Diarsaallendiide (AsCAs2-) Ligands Coordinated to Uranium and Generated via Activation of the Arsaethynolate Ligand (OCAs-)." Angewandte Chemie International Edition 58.6 (2019): 1679-1683.

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