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The “Si-2s- and Si-2p-binding energies” of 5 o-arylenedioxy complexes containing penta- and hexacoordinate silicon have been obtained from their ESCA-spectra. The data have been compared to those of tetracovalent silicon compounds. A linear correlation between calculated Pauling charges and binding energies has been found for compounds where no (d ← n) -interaction should exist. Characteristic deviations from the linear relation were found both in tetravalent silicon compounds containing Si-O-bonds, the (d ← n)π-interaction of which is well established, and in the anionic tris(o-phenylenedioxy) siliconate and in the bis(o-phenylenedioxy) organosiliconates. No deviations were observed in case of the cationic 6-coordinate complexes of silicon with acetylacetone and 2-hydroxypyridine-N-oxide. We conclude that an additional back donation from the free electron pair (d Si  ← n O o) only exists to a considerable extent in tetracovalent silicic ester derivatives, in the hexa- and pentacoordinate tris(o-phenylendioxy) siliconate and in the bis(o-phenylenedioxy) organosiliconates. A method is given to obtain crystalline tris(2-oxypyridine-N-oxy) siliconium chloride in good yield.

zeitschrift für naturforschung b

Zum Bindungszustand des fünf- und sechsbindigen Siliciums in kationischen und anionischen o-Arylendioxychelaten / (d ← n) π-Bonding in Anionic and Cationic o-Arylenedioxy Chelates of Hexacoordinate and Pentacoordinate Silicon Studied by Means of ESCA