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Acta Chimica Sinica >

2024 , Vol. 82 >Issue 5: 471 - 476

DOI: https://doi.org/10.6023/A24020060

Communication

Reactivities of Nonsymmetric PNN Pincer Cobalt Complex Under Reductive Conditions

  • Yuanjin Chen ,
  • Dajiang Huang ,
  • Xianghui Shi ,
  • Zhenfeng Xi ,
  • Junnian Wei
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  • Beijing National Laboratory for Molecular Sciences (BNLMS), Key Laboratory of Bioorganic Chemistry and Molecular Engineering of Ministry of Education, College of Chemistry and Molecular Engineering, Peking University, Beijing 100871, China
*E-mail: ; Tel.: 010-62755835

Received date: 2024-02-22

  Online published: 2024-04-10

Supported by

National Natural Science Foundation of China(21988101)

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Abstract

Nonsymmetric pincer complexes have received much attention due to their hemilability and more easily modulated spatial and electronic effects. However, their synthesis and reactivity studies remain considerably limited in comparison to symmetric pincer complexes. Common strategies to enhance the reactivity of complexes, such as reducing coordination sites or lowering metal center valences, invariably complicate synthesis. In this work, employing the strategy of introducing reducing agents, the PNNCoCl (1) (PNN: [6-(tBu2PN)C5H3N-2-(3-Mes)C3H2N2]) reacts with various small molecules to yield a variety of nonsymmetric pincer cobalt complexes, which were characterized by single-crystal X-ray diffractometry analysis and spectroscopy. The reaction of PNNCoCl, potassium graphite (or KHBEt3) with 1 equiv. of CNXyl (2,6-dimethylphenyl isocyanide) or carbon monoxide successfully yielded the monovalent cobalt complexes 2 (PNNCoCNXyl) and 3 (PNNCoCO) in 64% and 41% yields, respectively. Moreover, the reaction of complex 1 with N-heterocyclic carbene (1,3-diisopropyl-4,5-dimethyl-imidazol-2-ylidene), involving C—H bond cleavage and Co—C bond formation, afforded the corresponding divalent cobalt complex 4. Furthermore, by using different reducing agents, we achieved the modulation of the selective reaction of azobenzene C—H or N=N bonds. When KC8 (potassium graphite) was used as the reducing agent, the reaction of PNNCoCl and azobenzene in tetrahydrofuran afforded the azobenzene C—H bond-breaking product 5 in 53% yield. The cobalt atom is pentacoordinate in a tetragonal pyramid geometry. The N—N lengths of 0.12835(17) nm in complex 5 are in the range of normal N=N double bonds (0.122~0.130 nm). In contrast, the reaction of 1 with azobenzene in the presence of KHBEt3 gave the cobalt complex PNNCoNHPh (6), as confirmed by X-ray diffraction analysis. The structure suggests N=N double bond cleavage of azobenzene in the formation of the aniline complex. The N—H stretching bands of 6 were recorded at 3131 cm−1, and the solution magnetic moment was µeff=2.2 µB. In addition, the treatment of complex 1 with 3,5-di-tert-butyl-o-benzoquinone in the presence of 1.2 equiv. of KC8 gave rise to the cobalt complex 7. X-ray diffraction analysis of 7 revealed that the PNN ligand and o-benzoquinone parts are linked by forming a P—O single bond. The o-benzoquinone was reduced to the catechol ion. Complex 7 exhibits a high-spin electronic structure (S = 3/2), as evidenced by the solution magnetic moment of 4.0 µB.

Key words： pincer ligand; cobalt complex; small molecule activation; low-valent metal complex

Cite this article

Yuanjin Chen , Dajiang Huang , Xianghui Shi , Zhenfeng Xi , Junnian Wei . Reactivities of Nonsymmetric PNN Pincer Cobalt Complex Under Reductive Conditions[J]. Acta Chimica Sinica, 2024 , 82(5) : 471 -476 . DOI: 10.6023/A24020060

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