Z. Naturforsch. 2014, 69b, 1402 – 1418
New Insights into Hexacoordinated Silicon Complexes with 8-Oxyquinolinato Ligands: 1,3-Shift of Si-Bound Hydrocarbyl Substituents and the Influence of Si-Bound Halides on the 8-Oxyquinolinate Coordination Features
Erik Wächtler1, Alexander Kämpfe1, Katrin Krupinski1, Daniela Gerlach1, Edwin Kroke1, Erica Brendler2, and Jörg Wagler1
1 Institut für Anorganische Chemie, TU Bergakademie Freiberg, Leipziger Straße 29, 09596 Freiberg/Sachsen, Germany
2 Institut für Analytische Chemie, TU Bergakademie Freiberg, Leipziger Straße 29, 09596 Freiberg/Sachsen, Germany
Reprint requests to Dr. Jörg Wagler. Fax: (+49) 3731 39 4058. E-mail: joerg.wagler@chemie.tu-freiberg.de
Received August 1, 2014 / published online December 19, 2014
Dedicated to Professor Hubert Schmidbaur on the occasion of his 80th birthday
The transsilylation reaction between allyltrichlorosilane and 8-trimethylsiloxyquinoline in the molar ratio 1:3 yields the hexacoordinated silicon tris-chelate (oxinate)2Si(adho) (''oxinate'' = 8-oxyquinolinate, ''adho'' = di-anion of 2-allyl-1,2-dihydro-8-oxyquinoline) comprising an SiO3N3 skeleton. The identity of this complex was established by single-crystal X-ray diffraction analysis and 29Si CP/MAS NMR spectroscopy of its chloroform solvate. Benzyltrichlorosilane and dibenzyldichlorosilane, comprising benzyl (Bn) as an ''aromatically stabilized allyl moiety'' did not undergo such rearrangement. Instead, the complexes (oxinate)2SiBnCl and (oxinate)2SiBn2 were obtained even upon using three molar equivalents of 8-trimethylsiloxyquinoline.

We determined the crystal structure of a non-disordered bis-chelate (oxinate)2SiBnCl with Si-bound hydrocarbyl and halogen substituents (the previously published (oxinate)2SiMeCl was disordered with alternative Me/Cl site occupancies). (Oxinate)2SiBnCl exhibits surprisingly poor response of the N−Si bonds to the different trans-disposed Si−X (X = Bn, Cl) bonds. For comparison and deeper insights into the coordination chemistry of oxinato silicon complexes with halide substituents, we determined the crystal structures of (oxinate)2SiPhCl·CHCl3, (oxinate)2SiCl2, (oxinate)2SiF2 ·1.5(CHCl3), and (8-oxyquinaldinate)2SiF2. Furthermore, the crystal structures of BnSiCl3 and Bn2SiCl2 (and its dibromo analog) are reported. The influence of the Si–C–C–C torsion angles of the benzyl group on the 29Si NMR shift of benzylsilanes (which is noticeably upfield with respect to analogous methyl silanes) was analyzed by quantum-chemical calculations.

Key words: Benzylsilanes, Hypercoordination, Isomerism, Oxyquinolinate, Rearrangement
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