含碱土金属-金属键配合物的研究进展

doi:10.6023/cjoc202505024

摘要/Abstract

化学键的断裂和形成过程是化学领域中最重要的研究内容. 作为化学键的重要分支之一, 开展金属-金属键的研究对于人们深入理解物质的结构、成键特点以及催化转化本质等方面具有重要意义. 目前, 金属-金属键的研究主要集中在d区、p区以及f区金属, s区碱土金属因其电负性低、易失去外层电子而不易形成金属-金属键, 因此构建含碱土金属-金属键的配合物具有挑战. 结合该领域当前所取得的研究成果, 并根据成键元素的不同, 对已报道的含碱土金属-金属键配合物实例进行分类综述, 着重阐述其合成方法、结构以及碱土金属-金属键的性质. 最后, 对该研究领域的发展趋势和应用前景进行了展望.

关键词: 金属-金属键, 碱土金属, 金属配合物, 合成, 结构

The breaking and formation process of chemical bonds is the most important research content in the field of chemistry. As one of the most important branch of chemical bonds, the study of metal-metal bonds is of significant importance in further expanding our understanding of the structure of substances, the nature of the chemical bond and the essence of catalytic transformation. To date, the research of metal-metal bonds mainly focuses on d-block, p-block, and f-block elements. However, it is more difficult to form the metal-metal bonds due to the s-block alkaline earth metal elements with low electro- negativity can easily lose two valence electrons, resulting in the challenge of construction complexes containing alkaline earth metal-metal bonds. The recent progress in alkaline earth metal-metal bonds is reviewed, which are mainly focus on the synthesis, structure and reactivity of alkaline metal-metal bonds according to the different bonding elements. Finally, the future developments and applications in this field are also prospected.

Key words: metal-metal bond, alkaline earth metal, organometallic complex, synthesis, structure

引用此文

孙雄, 王顺林, 杨宇. 含碱土金属-金属键配合物的研究进展[J]. 有机化学, 2025, 45(12): 4315-4334.

Xiong Sun, Shunlin Wang, Yu Yang. Research Progress of Organometallic Complexes Containing Alkaline Earth Metal-Metal Bonds[J]. Chinese Journal of Organic Chemistry, 2025, 45(12): 4315-4334.

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图/表 39

图式1. β-二亚胺和胍基配体稳定的Mg(I)—Mg(I)键配合物的合成

Scheme 1. Synthesis of Mg(I)—Mg(I) bond complexes supported by β-diketiminate and guanidinate

图式2. Mg(I)—Mg(I) 键金属配合物与不饱和底物的反应性

Scheme 2. Reactivity of Mg(I)—Mg(I) bond complexes towards unsaturated substrates

图式3. 含氮多齿配体稳定的Mg(I)—Mg(I)键配合物的合成及反应性

Scheme 3. Synthesis and reactivity of Mg(I)—Mg(I) bond complexes supported by N-containing multidentate ligand

图式4. 膦亚胺配体稳定的Mg(I)—Mg(I)键配合物的合成

Scheme 4. Synthesis of Mg(I)—Mg(I) bond complex supported by diiminophosphinate ligand

图式5. 不对称β-二亚胺稳定的Mg(I)—Mg(I)键配合物的合成

Scheme 5. Synthesis of Mg(I)—Mg(I) bond complex supported by unsymmetrical β-diketiminate

图式6. β-二亚胺稳定的Mg(I)—Mg(I)键配合物在催化转化中的应用

Scheme 6. Application of Mg(I)—Mg(I) bond complexes supported by β-diketiminate in catalytic transformations

图式7. 大位阻β-二亚胺配体稳定的Mg(I)—Mg(I)键配合物的合成

Scheme 7. Synthesis of Mg(I)—Mg(I) bond complexes supported by superbulky β-diketiminate

图式8. 首例Mg(0)配合物的合成及反应性研究

Scheme 8. Synthesis and reactivity of the first Mg(0) complex

图式9. 手性β-二亚胺配体稳定的Mg(I)—Mg(I)键配合物的合成

Scheme 9. Synthesis of Mg(I)—Mg(I) bond complex supported by chiral β-diketiminate

图式10. Mg(I)—Mg(I)键配合物的合成

Scheme 10. Synthesis of complexes with the Mg(I)—Mg(I) bonds

图式11. 双阴离子配体稳定的Mg(I)二聚体的合成及其反应性

Scheme 11. Synthesis and reactivity of the dianionic Mg(I) dimers supported by double anionic ligands

图式12. Be—Be键配合物的合成

Scheme 12. Synthesis of complexes with the Be(I)—Be(I) bonds

图式13. Mg—Ae键配合物的合成及反应性

Scheme 13. Synthesis and reactivity of complexes with the Mg—Ae bonds

图式14. Mg(0)Na＋3环状配合物的合成及反应性

Scheme 14. Synthesis and reactivity of the cyclic Mg(0)Na＋3 complex

图1. 碱土金属-过渡金属键配合物

Figure 1. Complexes with alkaline earth metal-transition metal bonds

图式15. Mg—Fe和Mg—Co键金属配合物的合成

Scheme 15. Synthesis of complexes with the Mg—Fe and Mg—Co bonds

图式16. Mg—Fe和Mg—Co键金属配合物的合成及反应性

Scheme 16. Synthesis and reactivity of complexes with the Mg—Fe and Mg—Co bonds

图式17. Mg—Mn和Mg—Zn键配合物的合成

Scheme 17. Synthesis of complexes with the Mg—Mn and Mg—Zn bonds

图式18. Mg—Zn键配合物的合成及其反应性

Scheme 18. Synthesis and reactivity of complex with the Mg—Zn bond

图式19. Mg—Fe键配合物的合成及其反应性

Scheme 19. Synthesis and reactivity of complex with the Mg—Fe bond

图式20. Mg—Pd/Pt/Ni键配合物的合成及其反应性

Scheme 20. Synthesis and reactivity of complexes with the Mg—Pd/Pt/Ni bonds

图式21. Mg—Ni键配合物的合成及其反应性

Scheme 21. Synthesis and reactivity of complexes with the Mg—Ni bonds

图式22. Mg—Cu键配合物的合成及其反应性

Scheme 22. Synthesis and reactivity of complex with the Mg—Cu bond

图式23. Be—TM键配合物的合成

Scheme 23. Synthesis of complexes with the Be—TM bonds

图式24. Mg/Ca—Fe/Co键配合物的合成

Scheme 24. Synthesis of complexes with the Mg/Ca—Fe/Co bonds

图式25. 重碱土金属-Fe金属键配合物的合成

Scheme 25. Synthesis of complexes with the heavier alkaline earth metal-Fe bond

图式26. Mg—Ge/Sn键配合物的合成

Scheme 26. Synthesis of the Mg—Ge/Sn bond complexes

图式27. Mg/Be—Al键配合物的合成

Scheme 27. Synthesis of the Mg/Be—Al bond complexes

图式28. Mg—Al/Ga键配合物的合成

Scheme 28. Synthesis of the Mg—Al/Ga bond complexes

图式29. Mg—Al键配合物的合成

Scheme 29. Synthesis of the Mg—Al bond complexes

图式30. Mg/Ca—Al键配合物的合成及反应性

Scheme 30. Synthesis and reactivity of the Mg/Ca—Al bond complexes

图式31. Be—Al/Ga键配合物的合成及反应性

Scheme 31. Synthesis and reactivity of the Be—Al/Ga bond complexes

图式32. Mg—Al和Be—In键配合物的合成

Scheme 32. Synthesis of the Mg—Al and Be—In bond complexes

图式33. Al—Mg—Al键配合物的合成

Scheme 33. Synthesis of the Al—Mg—Al bond complexes

图2. 重碱土金属-主族金属键配合物

Figure 2. Heavier alkaline earth metal-main group metal-metal bond complexes

图式34. Ba—Sn键配合物的合成

Scheme 34. Synthesis of the Ba—Sn bond complexes

图式35. Mg/Ca—Sn键配合物的合成

Scheme 35. Synthesis of the Mg/Ca—Sn bond complexes

图式36. Mg/Ca—Ge键配合物的合成

Scheme 36. Synthesis of the Mg/Ca—Ge bond complexes

图式37. Mg—Sb键配合物的合成

Scheme 37. Synthesis of the Mg—Sb bond complexes

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