title: First Isolation and Characterization of the Highly Coordinated Group 14 Enolates: Effects of the Coordination Controls on the Geometry and Tautomerization of Germyl Enolates.
abstract: The Group 14 enolates play an important part in many organic reactions. Herein, the reduction of an α-bromo ketone with germanium(II) salts cleanly afforded the corresponding germyl enolate as an isolatable species. This experimental reductive generation of a germyl enolate enabled us to characterize both C- and O-bound tautomers derived from an identical precursor and to unveil the tautomeric mechanisms, including the kinetic parameters and the relative stability of these tautomers, along with confirmation from DFT calculations. Moreover, the highly coordinated germyl enolates were isolated by a stabilization process induced by adding ligands. All products were characterized by NMR spectroscopy and X-ray crystallography.
authors.affiliation: Department of Applied Chemistry, Graduate School of Engineering, Osaka University, 2-1 Yamadaoka, Suita, Osaka, 565-0871, Japan.|Center for Atomic and Molecular Technologies, Graduate School of Engineering, Osaka University, 2-1 Yamadaoka, Suita, Osaka, 565-0871, Japan.
authors.forename: Akihito
authors.initials: A
authors.lastname: Konishi
authors.affiliation: Department of Applied Chemistry, Graduate School of Engineering, Osaka University, 2-1 Yamadaoka, Suita, Osaka, 565-0871, Japan.
authors.forename: Yohei
authors.initials: Y
authors.lastname: Minami
authors.affiliation: Department of Applied Chemistry, Graduate School of Engineering, Osaka University, 2-1 Yamadaoka, Suita, Osaka, 565-0871, Japan.
authors.forename: Takahisa
authors.initials: T
authors.lastname: Hosoi
authors.affiliation: Science and Technology System Division, Ryoka Systems Inc., Tokyo Skytree East Tower, 1-1-2 Oshiage, Sumida-ku, Tokyo, 131-0045, Japan.
authors.forename: Kouji
authors.initials: K
authors.lastname: Chiba
authors.affiliation: Department of Applied Chemistry, Graduate School of Engineering, Osaka University, 2-1 Yamadaoka, Suita, Osaka, 565-0871, Japan. yasuda@chem.eng.osaka-u.ac.jp.
authors.forename: Makoto
authors.initials: M
authors.lastname: Yasuda
keywords: germanium; germyl enolate; highly coordinated enolate; reaction order; tautomerization