Reactivity of an arsanyl-phosphagallene: decarbonylation of CO<sub>2</sub> and COS to form phosphaketenes
The synthesis of an arsanyl-phosphagallene [H<sub>2</sub>CN(Dipp)]<sub>2</sub>AsP[double bond, length as m-dash]Ga(NacNac) (NacNac = HC[C(Me)N(Dipp)]<sub>2</sub>; Dipp = diisopropylphenyl) and its reactivity towards heterocumulenes and ketones is described. Reactions with azides, carbodiimides, isocyanates and ketones give rise to heterocycles <i>via</i> cyclization reactions involving the Ga[double bond, length as m-dash]P π-bond (with the Ga-P σ-bond remaining unperturbed in the final products). By contrast, reactions with CO<sub>2</sub>, CS<sub>2</sub> 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
- Jonas Bresien (ORCID: https://orcid.org/0000-0001-9450-3407)
- José M. Goicoechea (ORCID: https://orcid.org/0000-0002-7311-1663)
- Lilian Sophie Szych (ORCID: https://orcid.org/0000-0002-2445-6366)
- Moritz Ernst (ORCID: https://orcid.org/0000-0001-9505-8974)
- Lukas Fischer
Institutions
- Mansfield University (US)
- Oxford Research Group (GB)
- University of Oxford (GB)
- Indiana University Bloomington (US)
- University of Rostock (DE)
- Freie Universität Berlin (DE)
Publication Details
- Journal
- Chemical Science
- Published
- 2025-01-01
- DOI
- https://doi.org/10.1039/d5sc00295h
- Citations
- 8
- Primary Topic
- Synthesis and characterization of novel inorganic/organometallic compounds
- Type
- article
- Field-Weighted Citation Impact
- 4.30
Funders
- University of Oxford
- Freie Universität Berlin
- Universität Rostock
- Deutsche Akademie der Naturforscher Leopoldina - Nationale Akademie der Wissenschaften