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- Title
Photolytic and Reductive Activations of 2‐Arsaethynolate in a Uranium–Triamidoamine Complex: Decarbonylative Arsenic‐Group Transfer Reactions and Trapping of a Highly Bent and Reduced Form.
- Authors
Magnall, Rosie; Balázs, Gábor; Lu, Erli; Kern, Michal; Slageren, Joris; Tuna, Floriana; Wooles, Ashley J.; Scheer, Manfred; Liddle, Stephen T.
- Abstract
Little is known about the chemistry of the 2‐arsaethynolate anion, but to date it has exclusively undergone fragmentation reactions when reduced. Herein, we report the synthesis of [U(TrenTIPS)(OCAs)] (2, TrenTIPS=N(CH2CH2NSiiPr3)3), which is the first isolable actinide‐2‐arsaethynolate linkage. UV‐photolysis of 2 results in decarbonylation, but the putative [U(TrenTIPS)(As)] product was not isolated and instead only [{U(TrenTIPS)}2(μ‐η2:η2‐As2H2)] (3) was formed. In contrast, reduction of 2 with [U(TrenTIPS)] gave the mixed‐valence arsenido [{U(TrenTIPS)}2(μ‐As)] (4) in very low yield. Complex 4 is unstable which precluded full characterisation, but these photolytic and reductive reactions testify to the tendency of 2‐arsaethynolate to fragment with CO release and As transfer. However, addition of 2 to an electride mixture of potassium‐graphite and 2,2,2‐cryptand gives [{U(TrenTIPS)}2{μ‐η2(OAs):η2(CAs)‐OCAs}][K(2,2,2‐cryptand)] (5). The coordination mode of the trapped 2‐arsaethynolate in 5 is unique, and derives from a new highly reduced and bent form of this ligand with the most acute O‐C‐As angle in any complex to date (O‐C‐As ∠ ≈128°). The trapping rather than fragmentation of this highly reduced O‐C‐As unit is unprecedented, and quantum chemical calculations reveal that reduction confers donor–acceptor character to the O‐C‐As unit.
- Subjects
DECARBONYLATION; FRAGMENTATION reactions; CHEMISTRY
- Publication
Chemistry - A European Journal, 2019, Vol 25, Issue 62, p14246
- ISSN
0947-6539
- Publication type
Article
- DOI
10.1002/chem.201903973