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

The transsilylation reaction between allyltrichlorosilane and 8-trimethylsiloxyquinoline in the molar ratio 1 : 3 yields the hexacoordinated silicon tris-chelate (oxinate) Si(adho) (“oxinate” = 8- oxyquinolinate, “adho” = di-anion of 2-allyl-1,2-dihydro-8-oxyquinoline) comprising an SiO skeleton. The identity of this complex was established by single-crystal X-ray diffraction analysis and Si 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) SiBnCl and (oxinate) SiBn were obtained even upon using three molar equivalents of 8-trimethylsiloxyquinoline. We determined the crystal structure of a non-disordered bis-chelate (oxinate) SiBnCl with Sibound hydrocarbyl and halogen substituents (the previously published (oxinate) SiMeCl was disordered with alternative Me=Cl site occupancies). (Oxinate) SiBnCl 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) SiPhCl·CHCl , (oxinate) SiCl , (oxinate) SiF ·1.5(CHCl ), and (8-oxyquinaldinate) SiF . Furthermore, the crystal structures of BnSiCl and Bn SiCl (and its dibromo analog) are reported. The influence of the Si-C-C-C torsion angles of the benzyl group on the Si NMR shift of benzylsilanes (which is noticeably upfield with respect to analogous methyl silanes) was analyzed by quantum-chemical calculations.