Issue 22, 2018

Thermodynamic and reactivity studies of a tin corrole–cobalt porphyrin heterobimetallic complex

Abstract

A heterobimetallic complex, (TPFC)Sn–Co(TAP) (TPFC = 5,10,15-tris(pentafluorophenyl)corrole, TAP = 5,10,15,20-tetrakis(p-methoxyphenyl)porphyrin), was synthesized. The complex featured a Sn–Co bond with a bond dissociation enthalpy (BDE) of 30.2 ± 0.9 kcal mol−1 and a bond dissociation Gibbs free energy (BDFE) of 21.0 ± 0.2 kcal mol−1, which underwent homolysis to produce the (TPFC)Sn radical and (TAP)CoII under either heat or visible light irradiation. The novel tin radical (TPFC)Sn, being the first four-coordinate tin radical observed at room temperature, was studied spectroscopically and computationally. (TPFC)Sn–Co(TAP) promoted the oligomerization of aryl alkynes to give the insertion products (TPFC)Sn–(CH[double bond, length as m-dash]C(Ar))n–Co(TAP) (n = 1, 2, or 3) as well as 1,3,5-triarylbenzenes. Mechanistic studies revealed a radical chain mechanism involving the (TPFC)Sn radical as the key intermediate.

Graphical abstract: Thermodynamic and reactivity studies of a tin corrole–cobalt porphyrin heterobimetallic complex

Supplementary files

Article information

Article type
Edge Article
Submitted
18 Marts 2018
Accepted
30 Apr. 2018
First published
02 Maijs 2018
This article is Open Access

All publication charges for this article have been paid for by the Royal Society of Chemistry
Creative Commons BY-NC license

Chem. Sci., 2018,9, 4999-5007

Thermodynamic and reactivity studies of a tin corrole–cobalt porphyrin heterobimetallic complex

Z. Wang, Z. Yao, Z. Lyu, Q. Xiong, B. Wang and X. Fu, Chem. Sci., 2018, 9, 4999 DOI: 10.1039/C8SC01269E

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