CO2 cleavage by tantalum/M (M = iridium, osmium) heterobimetallic complexes

Abdelhak Lachguar; Christopher Z Ye; Sheridon N Kelly; Erwann Jeanneau; Iker Del Rosal; Laurent Maron; Laurent Veyre; Chloé Thieuleux; John Arnold; Clément Camp

doi:10.1039/d4cc02207f

CO₂ cleavage by tantalum/M (M = iridium, osmium) heterobimetallic complexes

Chem Commun (Camb). 2024 Jul 25;60(61):7878-7881. doi: 10.1039/d4cc02207f.

Authors

Abdelhak Lachguar¹, Christopher Z Ye^{2

3}, Sheridon N Kelly^{2

3}, Erwann Jeanneau⁴, Iker Del Rosal⁵, Laurent Maron⁵, Laurent Veyre¹, Chloé Thieuleux¹, John Arnold^{2

3}, Clément Camp¹

Affiliations

¹ Laboratory of Catalysis, Polymerization, Processes and Materials (CP2M UMR 5128) CNRS, Universite Claude Bernard Lyon 1, CPE-Lyon, Institut de Chimie de Lyon, 43 Bvd du 11 Novembre 1918, 69616 Villeurbanne, France. clement.camp@univ-lyon1.fr.
² Department of Chemistry, University of California, Berkeley, California 94720, USA. arnold@berkeley.edu.
³ Chemical Sciences Division, Lawrence Berkeley National Laboratory, Berkeley, California 94720, USA.
⁴ Centre de Diffractométrie Henri Longchambon, Universite Claude Bernard Lyon 1, 5 Rue de la Doua, 69100 Villeurbanne, France.
⁵ Université de Toulouse, CNRS, INSA, UPS, UMR5215, LCPNO, 135 Avenue de Rangueil, F-31077 Toulouse, France.

Abstract

A novel Ta/Os heterobimetallic complex, [Ta(CH₂tBu)₃(μ-H)₃OsCp*], 2, is prepared by protonolysis of Ta(CHtBu)(CH₂tBu)₃ with Cp*OsH₅. Treatment of 2 and its iridium analogue [Ta(CH₂tBu)₃(μ-H)₂IrCp*], 1, with CO₂ under mild conditions reveal the efficient cleavage of CO₂, driven by the formation of a tantalum oxo species in conjunction with CO transfer to the osmium or iridium fragments, to form Cp*Ir(CO)H₂ and Cp*Os(CO)H₃, respectively. This bimetallic reactivity diverges from more classical CO₂ insertion into metal-X (X = metal, hydride, alkyl) bonds.