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Reversible Hydride Migration from C₅Me₅ to Rh^I Revealed by a Cooperative Bimetallic Approach.

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 C₅Me₅ in [(?-C₅Me₅)Rh(PMe₃)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.

SUBMITTER: Alferez MG

PROVIDER: S-EPMC7754342 | biostudies-literature | 2020 Nov

REPOSITORIES: biostudies-literature

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Reversible Hydride Migration from C5Me5 to RhI Revealed by a Cooperative Bimetallic Approach.

Alférez Macarena G MG Moreno Juan J JJ Hidalgo Nereida N Campos Jesús J

Angewandte Chemie (International ed. in English) 20200909 47

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 C5Me5 in [(η-C5Me5)Rh(PMe3)2] to form a new Rh-H bond, a process so far restricted to early transition metals. Experimen ...[more]

PMID: 33448577

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