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Entrapment of THF‐Stabilized Iridacyclic Ir III Silylenes from Double H−Si Bond Activation and H 2 Elimination
Author(s) -
Binh Dang Ho,
Hamdaoui Mustapha,
FischerKrauser Diane,
Karmazin Lydia,
Bailly Corinne,
Djukic JeanPierre
Publication year - 2018
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.201804048
Subject(s) - silylene , chemistry , phenylsilane , adduct , cationic polymerization , reactive intermediate , medicinal chemistry , infrared spectroscopy , nuclear magnetic resonance spectroscopy , crystallography , oxidative addition , catalysis , stereochemistry , photochemistry , polymer chemistry , silicon , organic chemistry
The reaction of H 3 SiR (R=Ph, n Bu) with cationic η 5 ‐C 5 Me 5 ‐ (Cp*) and benzo[ h ]quinolinyl‐based iridacycle [ 1 b ] + gives rise to new [(IrH)→SiRH 2 ] + adducts. In the presence of THF these adducts readily undergo elimination of H 2 gas at subambient temperature to form THF‐stabilized metallacyclic Ir III silylene complexes, which were characterized in situ by NMR spectroscopy, trapped in minute amounts by reactive crystallization, and structurally characterized by XRD. Theoretical investigations (static DFT‐D reaction‐energy profiling, ETS‐NOCV) support the promoting role of THF in the H 2 elimination step and the consolidation of the Ir‐to‐Si interaction in the spontaneous (Δ G <0) formation of Ir silylenes in the presence of THF. Mechanistic insights indicate that the Ir silylene species arising from the [ 1 b ] + /phenylsilane system are relevant catalytic species in the hydrodefluorination of fluoroalkanes.