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

摘要

The transsilylation reaction between allyltrichlorosilane and 8-trimethylsiloxyquinoline in the molar ratio 1: 3 yields the hexacoordinated silicon tris-chelate (oxinate)2Si(adho) ("oxinate" = 8oxyquinolinate, "adho" = di-anion of 2-allyl-1,2-dihydro-8-oxyquinoline) comprising an S1O3N3 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)(2)SiBnCl and (oxinate)(2)SiBn2 were obtained even upon using three molar equivalents of 8-trimethylsiloxyquinoline.