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The Synthesis of [Sn10(Si(SiMe3)3)4]2- Using a Metastable Sn(I) Halide Solution Synthesized via a Co-condensation Technique
Published on: November 28, 2016
Synthesis and Electrochemistry of Tin(IV) Octaethylcorroles, (OEC)Sn(C(6)H(5)) and (OEC)SnCl
Karl M. Kadish1, Stefan Will, Victor A. Adamian
1Department of Chemistry, University of Houston, Houston, Texas 77204-5641, and Institut für Organische Chemie, Universität zu Köln, Greinstrasse 4, 50939 Köln, Germany.
Abstract:
Two Sn(IV) corroles were synthesized and electrochemically examined. The investigated compounds are represented as (OEC)Sn(C(6)H(5)) and (OEC)SnCl, where OEC = trianion of 2,3,7,8,12,13,17,18-octaethylcorrole. (OEC)Sn(C(6)H(5)) represents the first example of a sigma-bonded metallocorrole which does not undergo a metal-centered electrode reaction. Both compounds undergo three reversible one-electron oxidations, all of which occur at the conjugated macrocycle. The reduction of (OEC)SnCl involves an overall two electrons, with the product being spectroscopically identified as a Sn(II) corrole after bulk electrolysis of the starting compound. (OEC)Sn(C(6)H(5)) is reversibly reduced by a single electron to give a Sn(IV) corrole pi-anion radical. The electrochemically measured HOMO-LUMO gap (defined as the absolute potential difference between the first-ring centered reduction and first ring-centered oxidation) is equal to 2.25 V in benzonitrile, a value which closely approximates what is observed for porphyrins containing octaethylporphyrin (OEP) or tetraphenylporphyrin (TPP) macrocycles. An X-ray crystallographic analysis for the molecular structure of (OEC)Sn(C(6)H(5)) is also presented: monoclinic, P2(1)/n, with a = 13.235(4) Å, b = 14.502(4) Å, c = 18.387(5) Å, beta = 95.45(2) degrees, Z = 4, R = 0.0619.
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