Reactivity of an arsanyl-phosphagallene: decarbonylation of CO 2 and COS to form phosphaketenes † ‡

Journal article

The synthesis of an arsanyl-phosphagallene [H2CN(Dipp)]2AsP 00000000 00000000 00000000 00000000 11111111 00000000 11111111 00000000 00000000 00000000 Ga(NacNac) (NacNac = HC[C(Me)N(Dipp)]2; Dipp = diisopropylphenyl) and its reactivity towards heterocumulenes and ketones is described. Reactions with azides, carbodiimides, isocyanates and ketones give rise to heterocycles via cyclization reactions involving the GaP π-bond (with the Ga–P σ-bond remaining unperturbed in the final products). By contrast, reactions with CO2, CS2 and COS are more intriguing, revealing a reactivity profile in which the phosphorus atom can abstract carbon monoxide from the oxygen-containing heterocumulenes. These reactions result in the formation of gallium phosphaethynolate compounds. Such reactivity is enabled by the presence of a weakly Lewis basic arsanyl moiety which, in contrast to other related compounds featuring phosphanyl groups, is insufficiently nucleophilic to play a role in frustrated Lewis-pair like reactivity.

Authors: Szych, LS; Bresien, J; Fischer, L; Ernst, MJ; Goicoechea, JM

• Publication status: Published
• Peer review status: Peer reviewed
• Publisher: Royal Society of Chemistry
• Journal: Chemical Science
• Publication date: 2025-03-17
• Acceptance date: 2025-03-14
• DOI: 10.1039/d5sc00295h
• EISSN: 2041-6539
• ISSN: 2041-6520
• Language: English