Cyaarside (CAs−) and 1, 3‐Diarsaallendiide (AsCAs2−) Ligands Coordinated to Uranium and Generated via Activation of the Arsaethynolate Ligand (OCAs−). (9th January 2019)

• Record Type: Journal Article
• Authors: Hoerger, Christopher J.; Heinemann, Frank W.; Louyriac, Elisa; Rigo, Massimo; Maron, Laurent; Grützmacher, Hansjörg; Driess, Matthias; Meyer, Karsten
• Is Part Of: Angewandte Chemie. Volume 131:Number 6(2019)
• Page Start: 1693
• Page End: 1697
• Publication Date: 2019-01-09
• Subjects: Arsaethinolat -- Arsen -- Diarsaallen -- Kohlenstoff-Arsen-Dreifachbindungen -- Uran; Chemistry -- Periodicals; 540
• DOI: 10.1002/ange.201811332
• Languages: English
• ISSNs: 0044-8249

Abstract

Abstract: Reaction of the trivalent uranium complex [(( Ad, Me ArO)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)][{(( Ad, Me ArO)3 N)U IV (THF)}(μ‐O){(( Ad, Me ArO)3 N)U IV (CAs)}] (1 ), the first example of a coordinated η 1 ‐cyaarside ligand (CAs − ). Formation of the terminal CAs − is promoted by the highly reducing, oxophilic U III precursor [(( Ad, Me ArO)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, μ‐oxo‐bridged U2 IV/IV complex [Na(2.2.2‐crypt)]2 [{(( Ad, Me ArO)3 N)U IV }2 (μ‐O)(μ‐AsCAs)] (2 ), comprising the hitherto unknown μ:η 1, η 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 − . Abstract : As statt N : Eine stark reduzierende oxophile U III ‐Vorstufe reagiert mit Arsaethinolat (OCAs − ) zu zweikernigen Urankomplexen mit neuartigem η 1 ‐gebundenem Cyaarsid‐Ligand (CAs − ) und beispiellosem Diarsaallendiid(AsCAs 2− )‐Brückenligand. Der CAs − ‐Ligand ist das schwerste bisher bekannte Cyanid‐Analogon.