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Issue 22, 2018
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Thermodynamic and reactivity studies of a tin corrole–cobalt porphyrin heterobimetallic complex

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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

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Publication details

The article was received on 18 Mar 2018, accepted on 30 Apr 2018 and first published on 02 May 2018


Article type: Edge Article
DOI: 10.1039/C8SC01269E
Citation: Chem. Sci., 2018,9, 4999-5007
  • Open access: Creative Commons BY-NC license
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    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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