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Communication

An Antiaromatic Porphyrin Complex: Tetraphenylporphyrinato(silicon)(L)₂ (L = THF or Pyridine)

Supporting Info

Julie A. Cissell,^‡ Thomas P. Vaid,*^‡ and Arnold L. Rheingold^§

Center for Materials Innovation and Department of Chemistry, Washington University, St. Louis, Missouri 63130, and Department of Chemistry, University of California, San Diego, La Jolla, California 92093

J. Am. Chem. Soc., 2005, 127 (35), pp 12212–12213

DOI: 10.1021/ja0544713

Publication Date (Web): August 16, 2005

‡

Washington University in St. Louis.

In papers with more than one author, the asterisk indicates the name of the author to whom inquiries about the paper should be addressed.

University of California, San Diego.

, vaid@wustl.edu

Abstract

Treatment of Si(TPP)Cl₂ (TPP = tetraphenylporphyrinato) with 2 equiv of Na/Hg in THF yields the reduced porphyrin complex, Si(TPP)(THF)₂, in which the porphyrin ring system has an oxidation state of 4− and the complex is antiaromatic. Single-crystal X-ray diffraction reveals that Si(TPP)(THF)₂ is highly ruffled and exhibits a unique C−C bond length alternation around its periphery. In addition, experimental ¹H and ²⁹Si NMR chemical shifts and NICS (nucleus-independent chemical shift) calculations on a model compound indicate a strong paratropic ring current in Si(TPP).

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