Capturing the Organic Species Derived from the C-C Cleavage and in Situ Oxidation of 1,2,3,4-Tetra(pyridin-4-yl)cyclobutane by [CuCN] n-Based MOFs

Liang Chen; Hong-Xi Li; Ming Dai; Hai-Yan Li; Jian-Ping Lang

doi:10.1021/acs.inorgchem.8b01171

Capturing the Organic Species Derived from the C-C Cleavage and in Situ Oxidation of 1,2,3,4-Tetra(pyridin-4-yl)cyclobutane by [CuCN] _n-Based MOFs

Inorg Chem. 2018 Aug 6;57(15):9160-9166. doi: 10.1021/acs.inorgchem.8b01171. Epub 2018 Jul 25.

Authors

Liang Chen^{1

2}, Hong-Xi Li¹, Ming Dai³, Hai-Yan Li¹, Jian-Ping Lang^{1

2}

Affiliations

¹ State and Local Joint Engineering Laboratory for Novel Functional Polymeric Materials, College of Chemistry, Chemical Engineering and Materials Science , Soochow University , Suzhou 215123 , Jiangsu , P. R. China.
² State Key Laboratory of Organometallic Chemistry , Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences , Shanghai 200032 , P. R. China.
³ Suzhou Clean Environment Institute , Jiangsu Sujing Group Co., Ltd. , Suzhou 215122 , Jiangsu , China.

PMID: 30044612
DOI: 10.1021/acs.inorgchem.8b01171

Abstract

The solvothermal cycloreversion and in situ oxidation of 1,2,3,4-tetra(pyridin-4-yl)cyclobutane (tpcb) within [CuCN] _n-based MOFs were investigated. The radical mechanism for the cycloreversion of tpcb ligands was supported by capturing a 1,3-butadiene species 1,2,3,4-tetra(4-pyridyl)-1,3-butadiene (tpyb) into {[Cu₁₈(μ-CN)₁₈(tpcb)₄(tpyb)₂]·H₂O} _n in the presence of 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO). Without TEMPO, a furan-based ligand 2,3,4,5-tetra(4-pyridyl)furan (tpyf) was generated within {[Cu₄(μ-CN)₄(tpyf)]·4MeCN} _n via the C-C cleavage, followed by in situ oxidation in acidic condition.