Citation: Yuanjin Chen, Yaqi Zhao, Xianghui Shi, Qiong Yuan, Rui Feng, Zhenfeng Xi, Junnian Wei. Cyclo-tetramerization of isocyanides promoted by cyclopentadienyl chromium complexes[J]. Chinese Chemical Letters, ;2025, 36(12): 111130. doi: 10.1016/j.cclet.2025.111130 shu

Cyclo-tetramerization of isocyanides promoted by cyclopentadienyl chromium complexes

Yuanjin Chen ^a ,
Yaqi Zhao ^a ,
Xianghui Shi ^a ,
Qiong Yuan ^a ,
Rui Feng ^a ,
Zhenfeng Xi ^{a, b} ,
Junnian Wei ^{a, *,}

a.
Beijing National Laboratory for Molecular Sciences (BNLMS), Key Laboratory of Bioorganic Chemistry and Molecular Engineering of Ministry of Education, College of Chemistry, Peking University, Beijing 100871, China
b.
State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Shanghai 200032, China

jnwei@pku.edu.cn

Received Date: 26 November 2024
Revised Date: 13 March 2025
Accepted Date: 20 March 2025
Available Online: 21 March 2025

Figures(16)

The reductive cyclocoupling of isocyanides is a pivotal reaction that facilitates the rapid construction of intricate cyclic compounds in a single-step process. In this work, treatment of simple precursor 1 (Cp^#CrLCl, L = CAAC, NHC, PCy₃, or PPh₂Et; Cp^# = Cp* or Cp*^TMS) with XylNC (2,6-dimethylphenyl isocyanide) led to the reductive coupling of isocyanides, yielding either complex 2 {(Cp*^TMSCr)₂[μ-C₄(NXyl)₄]} or complex 6 {(Cp*CrCl)₂[μ-C₄(NXyl)₄]}, corresponding to the tetramerization of isocyanides. Control experiments and in-situ monitoring were carried out to understand the reaction mechanism, revealing various side reaction pathways during the isocyanide tetramerization. SQUID and DFT calculations provided insights into the electronic structures. In complex 2, the energies of nonet and broken-symmetry singlet states are close and significantly lower than other spin states, indicating two independent high-spin Cr(Ⅱ) centers with weak antiferromagnetic coupling. A similar situation is observed in complex 6, where two independent high-spin Cr(Ⅲ) centers are coupled antiferromagnetically. In both complexes 2 and 6, the tetrameric isocyanide rings, receiving two electrons from Cr centers, show averaged bond lengths and display moderate aromatic characteristics.
- Cyclo-oligomerization,
- Isocyanide tetramerization,
- Chromium complex,
- Chromium chemistry
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