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Chemistry : A European Journal [LCSOM]

Sep 19 2018

Abstract :

The reaction of H₃SiR (R=Ph, nBu) with a cationic Cp*‐and benzo[h]quinolinyl‐ based iridacycle [1b]+ gives rise to new [(Ir‐H)→SiRH₂]+ adducts. In the presence of tetrahydrofuran (THF) the latter adducts readily convert by H₂ gas elimination at subambient temperature into new THF‐stabilized metallacyclic Ir(III)‐“silylene” complexes that were characterized in situ by NMR spectroscopic analyses, trapped in minute amount by reactive crystallization and their structures established by X‐ray diffraction analysis. Theoretical investigations (static DFT‐D reaction energy profiling, ETS‐NOCV) support the promoting role of THF in the H₂ elimination step and the consolidation of the Ir‐to‐Si interaction in the spontaneous (ΔG

Reference :

Dang Ho Binh, Mustapha Hamdaoui, Diane Fischer Krauser, Lydia Karmazin, Corinne Bailly, and Jean-Pierre Djukic

Entrapment of THFstabilized Iridacyclic Ir(III)“Silylenes” from Double HSi Bond Activation and H2 Elimination

 Chemistry : A European Journal, first published : 17 September 2018 - DOI : http://dx.doi.org/10.1002/chem.201804048.

Contact chercheur :

Jean-Pierre Djukic, LCSOM, Institut de Chimie (UMR 7177).