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

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(Tren^TIPS )(OCAs)] (2, Tren^TIPS =N(CH₂ CH₂ NSiiPr₃ )₃ ), which is the first isolable actinide-2-arsaethynolate linkage. UV-photolysis of 2 results in decarbonylation, but the putative [U(Tren^TIPS )(As)] product was not isolated and instead only [{U(Tren^TIPS )}₂ (μ-η² :η² -As₂ H₂ )] (3) was formed. In contrast, reduction of 2 with [U(Tren^TIPS )] gave the mixed-valence arsenido [{U(Tren^TIPS )}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(Tren^TIPS )}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 <mml:math xmlns:mml="http://www.w3.org/1998/Math/MathML"><mml:mi>∠</mml:mi></mml:math> ≈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.