Reversible Hydride Migration from C 5 Me 5 to Rh I Revealed by a Cooperative Bimetallic Approach

• Published in: Angewandte Chemie Vol. 132; no. 47; pp. 21049 - 21053
• Main Authors: Alférez, Macarena G., Moreno, Juan J., Hidalgo, Nereida, Campos, Jesús
• Format: Journal Article
• Language: English
• Published: 16-11-2020
• ISSN: 0044-8249; 1521-3757
• DOI: 10.1002/ange.202008442

Abstract
The use of cyclopentadienyl ligands in organometallic chemistry and catalysis is ubiquitous, mostly due to their robust spectator role. Nonetheless, increasing examples of non‐innocent behaviour are being documented. Here, we provide evidence for reversible intramolecular C−H activation at one methyl terminus of C
5
Me
5
in [(
η
‐C
5
Me
5
)Rh(PMe
3
)
2
] to form a new Rh−H bond, a process so far restricted to early transition metals. Experimental evidence was acquired from bimetallic rhodium/gold structures in which the gold center binds either to the rhodium atom or to the activated Cp* ring. Reversibility of the C−H activation event regenerates the Rh
I
and Au
I
monometallic precursors, whose cooperative reactivity towards polar E−H bonds (E=O, N), including the N−H bonds in ammonia, can be understood in terms of bimetallic frustration.