Reactivity of an arsanyl-phosphagallene: decarbonylation of CO2 and COS to form phosphaketenes

Lilian S. Szych; Jonas Bresien; Lukas Fischer; Moritz J. Ernst; Jose M. Goicoechea

doi:10.1039/D5SC00295H

Reactivity of an arsanyl-phosphagallene: decarbonylation of CO₂ and COS to form phosphaketenes†‡

Lilian S. Szych,

^ab Jonas Bresien,

^c Lukas Fischer,

^b Moritz J. Ernst

^b and Jose M. Goicoechea

*^d

Author affiliations

* Corresponding authors

^a Department of Chemistry, University of Oxford, Chemistry Research Laboratory, 12 Mansfield Road, Oxford, UK

^b Institut für Chemie und Biochemie, Freie Universität Berlin, Fabeckstraße 34/36, Berlin, Germany

^c Institut für Chemie, Universität Rostock, Albert-Einstein-Straße 3a, Rostock, Germany

^d Department of Chemistry, Indiana University, Bloomington, 800 E. Kirkwood Ave., Bloomington, IN, USA
E-mail: jgoicoec@iu.edu

Abstract

The synthesis of an arsanyl-phosphagallene [H₂CN(Dipp)]₂AsP [double bond, length as m-dash] 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 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 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.

Supplementary files

Article information

DOI: https://doi.org/10.1039/D5SC00295H
Article type: Edge Article
Submitted: 13 Jan 2025
Accepted: 14 Mar 2025
First published: 17 Mar 2025
This article is Open Access

All publication charges for this article have been paid for by the Royal Society of Chemistry

Download Citation

Chem. Sci., 2025,16, 7397-7410

Permissions

Request permissions

Reactivity of an arsanyl-phosphagallene: decarbonylation of CO₂ and COS to form phosphaketenes

L. S. Szych, J. Bresien, L. Fischer, M. J. Ernst and J. M. Goicoechea, Chem. Sci., 2025, 16, 7397 DOI: 10.1039/D5SC00295H

This article is licensed under a Creative Commons Attribution 3.0 Unported Licence. You can use material from this article in other publications without requesting further permissions from the RSC, provided that the correct acknowledgement is given.

Chemical Science