ChemRxiv
These are preliminary reports that have not been peer-reviewed. They should not be regarded as conclusive, guide clinical practice/health-related behavior, or be reported in news media as established information. For more information, please see our FAQs.
1/1
7 files

Dehydrogenative Double C—H Bond Activation in a Germylene-Rhodium Complex

preprint
submitted on 20.05.2021, 05:46 and posted on 24.05.2021, 13:37 by Sonia Bajo, Maria M. Alcaide, Joaquin López-Serrano, Jesus Campos
Transition metal tetrylene complexes offer great opportunities for molecular cooperation due to the ambiphilic character of the group 14 element. Here we focus on the coordination of germylene [(ArMes2)2Ge:] (ArMes = C6H3-2,6-(C6H2-2,4,6-Me3)2) to [RhCl(COD)]2 (COD = 1,5-cyclooctadinene), which yields a neutral germyl complex in which the rhodium center exhibits both η6- and η2-coordination to two mesityl rings in an unusual pincer-type structure. Chloride abstraction from this species triggers a singular dehydrogenative double C—H bond activation across the Ge/Rh motif. We have isolated and fully characterized three rhodium-germyl species associated to three C—H cleavage events along this process. The reaction mechanism has been further investigated by computational means, supporting the key cooperative action of rhodium and germanium centers.Transition metal tetrylene complexes offer great opportunities for molecular cooperation due to the ambiphilic character of the group 14 element. Here we focus on the coordination of germylene [(ArMes2)2Ge:] (ArMes = C6H3-2,6-(C6H2-2,4,6-Me3)2) to [RhCl(COD)]2 (COD = 1,5-cyclooctadinene), which yields a neutral germyl complex in which the rhodium center exhibits both η6- and η2-coordination to two mesityl rings in an unusual pincer-type structure. Chloride abstraction from this species triggers a singular dehydrogenative double C—H bond activation across the Ge/Rh motif. We have isolated and fully characterized three rhodium-germyl species associated to three C—H cleavage events along this process. The reaction mechanism has been further investigated by computational means, supporting the key cooperative action of rhodium and germanium centers.

History

Email Address of Submitting Author

jesus.campos@iiq.csic.es

Institution

Spanish National Research Council (CSIC)-University of Sevilla

Country

Spain

ORCID For Submitting Author

0000-0002-5155-1262

Declaration of Conflict of Interest

The authors declare no conflict of interest