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Efficient CO 2 Insertion and Reduction Catalyzed by a Terminal Zinc Hydride Complex
Author(s) -
Tüchler Michael,
Gärtner Lisa,
Fischer Susanne,
Boese A. Daniel,
Belaj Ferdinand,
MöschZanetti Nadia C.
Publication year - 2018
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.201801800
Subject(s) - chemistry , hydride , silanes , zinc , formate , hydrosilylation , catalysis , electrophile , lewis acids and bases , density functional theory , crystallography , ligand (biochemistry) , inorganic chemistry , medicinal chemistry , computational chemistry , silane , organic chemistry , metal , biochemistry , receptor
The terminal zinc hydride complex [Tntm]ZnH ( 2 ; Tntm=tris(6‐tert‐butyl‐3‐thiopyridazinyl)methanide) is an efficient hydrosilylation catalyst of CO 2 at room temperature without the need of Lewis acidic additives. The inherent electrophilicity of the system leads to selective formation of the monosilylated product (MeO) 3 SiO 2 CH (at room temperature with a TOF of 22.2 h −1 and at 45 °C with a TOF of 66.7 h −1 ). In absence of silanes, the intermediate formate complex [Tntm]Zn(O 2 CH) ( 3 ) is quantitatively formed within 5 min. All complexes were fully characterized by 1 H and 13 C NMR spectroscopy and single‐crystal X‐ray diffraction analyses. Density functional theory (DFT) calculations reveal a high positive charge on zinc and the increased preference of the ligand to adopt a κ 3 ‐coordination mode.