Synthesis and Structural Characterization of Novel Neutral Hexacoordinate Silicon(IV) Complexes with SiS₂O₂N₂ Skeletons

Abstract

A series of novel hexacoordinate silicon(IV) complexes with two tridentate dianionic S,N,O ligands was synthesized, starting from Si(NCO)4. All the compounds synthesized were structurally characterized by single‐crystal X‐ray diffraction and/or solid‐state NMR spectroscopy. In addition, most of the compounds were characterized by solution NMR spectroscopy.(© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008)

Ylenes in the MII→SiIV (M=Si, Ge, Sn) Coordination Mode

“…Furthermore, it provides the first example of a structurally characterized oligosilane bearing two neighboring hexacoordinate Si atoms, [14] and it represents the first crystallographically evidenced hexacoordinate Si compound where the coordination sphere comprises more than two chalcogen atoms heavier than oxygen. [15] As found for 1 and 2, the effect of merely limited Si1ÀM bond lengthening upon Si1 hexacoordination is encountered in 3 a: the Si1 À Si2 bond is only 0.04 longer than the Si2 À Si3 bond.…”

Crystal structure of dichlorido bis(2-methylbenzothiazole-κ 1N)palladium( II) chloride, C16H14Cl2N2PdS2

“…However the cyclization process to form benzothiazoles often prevents the formation of these types of ligands [11][12][13]. Even by overcoming these synthetic difficulties, there are somesilicon(IV) complexes of thiophenol-imine which have been reported previously [14]. However, we succeeded in forming the benzothiazole moiety and consequently, upon reaction with palladium acetate, obtained crystals of the title complex.…”

Disilicon Complexes with Two Hexacoordinate Si Atoms: Paddlewheel‐Shaped Isomers with (ClN4)SiSi(S4Cl) and (ClN2S2)SiSi(S2N2Cl) Skeletons

“…The use of chelating ligands or buttressing ligands has proved successful in forcing “unusual” donor atoms into the Si coordination sphere (Scheme ) 4a. u, ac, 5h In addition, methimazolide (mt − ) as a buttressing ligand has been proved capable of stabilizing the SiSi bond between two hexacoordinate (distorted octahedrally coordinated) Si atoms ( F ; Scheme ) 3a. In our mt‐stabilized Si complexes (i.e., E and F ),3a, 5a,b,d we noticed that the buttressing four N,S‐heterobidentate mt ligands furnished paddlewheel‐shaped complexes of the so‐called (4,0) isomer (Scheme ), that is, with four donor atoms of the same type attached to the same central atom.…”