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Dehydrogenative Double C−H Bond Activation in a Germylene‐Rhodium Complex **
Author(s) -
Bajo Sonia,
Alcaide María M.,
LópezSerrano Joaquín,
Campos Jesús
Publication year - 2021
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.202102529
Subject(s) - rhodium , pincer movement , chemistry , stereochemistry , bond cleavage , 1,5 cyclooctadiene , double bond , reductive elimination , medicinal chemistry , crystallography , catalysis , polymer chemistry , organic chemistry
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 [(Ar Mes2 ) 2 Ge :] (Ar Mes =C 6 H 3 ‐2,6‐(C 6 H 2 ‐2,4,6‐Me 3 ) 2 ) to [RhCl(COD)] 2 (COD=1,5‐cyclooctadiene), which yields a neutral germyl complex in which the rhodium center exhibits both η 6 ‐ and η 2 ‐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.