Recent Advances in the Synthesis, Structural Characterization, and Reactivity of Zero-Valent Main Group Compounds★

doi:10.6023/A25080274

Acta Chimica Sinica ›› 2025, Vol. 83 ›› Issue (12): 1576-1591.DOI: 10.6023/A25080274 Previous Articles Next Articles

Special Issue: “中国青年化学家”合辑

Review

零价态主族元素化合物的合成、结构与反应性质研究进展^★

陈明, 莫贞波^*()

南开大学化学学院元素有机化学全国重点实验室有机新物质创造前沿科学中心天津 300071

投稿日期:2025-08-06 发布日期:2025-10-10

作者简介:

陈明, 南开大学化学学院2022级在读博士研究生, 主要研究方向为低价主族元素化学及小分子活化.

莫贞波, 博士, 南开大学化学学院研究员, 博士生导师. 长期从事主族元素化学和金属有机化学方向的研究工作, 在新型低价态主族元素化合物的合成方面取得了一系列研究成果, 迄今在Chem、J. Am. Chem. Soc.、Angew. Chem. Int. Ed.、Nat. Commun.等国际著名期刊杂志发表学术论文40余篇.

^★ “中国青年化学家”专辑.

基金资助:
国家重点研发计划项目(2023YFF0723900); 国家自然科学基金项目(22071124); 国家自然科学基金项目(22371130); 国家自然科学基金项目(223B2109); 国家自然科学基金项目(22188101); 国家自然科学基金项目(22221002); 南开大学新有机质前沿科学研究中心项目(C029215001); 中央高校基本科研业务费专项资金(63206007); 南开大学

Recent Advances in the Synthesis, Structural Characterization, and Reactivity of Zero-Valent Main Group Compounds^★

Ming Chen, Zhenbo Mo^*()

State Key Laboratory of Elemento-organic Chemistry, Frontiers Science Center for New Organic Matter, College of Chemistry, Nankai University, Tianjin 300071

Received:2025-08-06 Published:2025-10-10
Contact: * E-mail: zhenbo.mo@nankai.edu.cn
About author:
^★ For the VSI “Rising Stars in Chemistry”.
Supported by:
National Key R&D Program of China(2023YFF0723900); National Natural Science Foundation of China(22071124); National Natural Science Foundation of China(22371130); National Natural Science Foundation of China(223B2109); National Natural Science Foundation of China(22188101); National Natural Science Foundation of China(22221002); Frontiers Science Center for New Organic Matter at Nankai University(C029215001); Fundamental Research Funds for the Central Universities(63206007); Nankai University.

Zero-valent main group elements give rise to a diverse array of allotropes through various bonding modes, such as covalent network bonding, molecular aggregation and polymeric chain formation. This structural diversity not only reflects the intrinsic bonding flexibility of these elements but also showcases their significant application potential in synthetic chemistry and the development of advanced new materials. In recent years, with the rapid advancement of main group element chemistry, ligand-stabilized low-valent main group element compounds have garnered increasing attention. Compounds containing zero-valent main group elements feature electron-rich main group element centers and exhibit extremely high reactivity, making their stable existence difficult to achieve for a long time. With the design and development of novel ligands for low-valent main group elements, a series of groundbreaking zero-valent main group element compounds have been successfully synthesized and characterized. Among these, ligand-stabilized mono- and dinuclear zero-valent main group element compounds exhibit unique electronic structures, and their isolation and characterization enhance our understanding of the bonding mechanisms associated with zero-valent main group elements. Since the differences in the electronic properties of ligands significantly affect the bonding modes between zero-valent element atoms and ligands, such compounds usually exhibit unique electronic structural characteristics and a rich variety of chemical reactivities. Furthermore, their excellent solub ility in common organic solvents greatly broadens their applications in homogeneous synthetic chemistry. Additionally, due to the unusual oxidation states of the central elements, zero-valent main group element compounds show promise in small molecule activation. This review mainly summarizes the synthesis of zero-valent compounds of elements from Group 13 to 15 in the p-block of the periodic table as well as a few alkaline earth metal elements in the s-block. The article elaborates on their isolation, electronic structures and bonding modes, and unique chemical reaction properties while addressing the challenges they face in this field and outlining future development directions.

Key words: main group elements chemistry, zero-valent, ligand, synthetic chemistry, small molecules activation

Cite this article

Ming Chen, Zhenbo Mo. Recent Advances in the Synthesis, Structural Characterization, and Reactivity of Zero-Valent Main Group Compounds^★[J]. Acta Chimica Sinica, 2025, 83(12): 1576-1591.

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Fig. & Tab. 45

Scheme 1. The coordination modes of carbenes and their heavy-element analogues stabilized zero-valent main group elements compound

Scheme 2. Synthesis and reactivity of CAAC-stabilized zero-valent beryllium compound (2)

Scheme 3. Synthesis of zero-valent magnesium compound (6)

Scheme 4. Reactivity of zero-valent magnesium compound (6) and (7)

Scheme 5. Synthesis of NHC-stabilized diatomic zero-valent boron compound (11)

Scheme 6. Reactivity of compound 11

Scheme 7. Synthesis of CAAC-stabilized diatomic boron compound (15)

Scheme 8. Reactivity of compound (11) and (15)

Scheme 9. Synthesis of IMe4-stabilized diatomic zero-valent boron compound (21)

Scheme 10. Reactivity of compound (21)

Scheme 11. Synthesis and reactivity of silylene-stabilized diatomic zero-valent boron compound (24)

Scheme 12. Synthesis and reactivity of CAAC-stabilized monoatomic zero-valent boron compound (28)

Scheme 13. Structure formula of Ph3P-stabilized monoatomic zero-valent carbon compound (31)

Scheme 14. Synthesis of NHC-stabilized monoatomic zero-valent carbon compound (33)

Scheme 15. Reactivity of zero-valent carbon compound (35)

Scheme 16. Reactivity of zero-valent carbon compound 37

Scheme 17. Synthesis of Ph3PCN2 (44) and Ph2SCN2 (47)

Scheme 18. Reactivity of CAAC-stabilized diatomic zero-valent carbon compound (48)

Scheme 19. Reactivity of phosphine-stabilized monocoordinated diatomic carbon compound (51)

Scheme 20. Synthesis of silylene-stabilized acyclic monoatomic zero-valent silicon compound 57 (a) and 60 (b)

Scheme 21. Synthesis of CAAC-stabilized monoatomic zero-valent silicon compound (62)

Scheme 22. Reactivity of NHC-stabilized monoatomic zero-valent silicon compound (63)

Scheme 23. Synthesis and reactivity of mesoionic carbene-stabilized monoatomic zero-valent silicon compound (69)

Scheme 24. Reactivity of silylene-stabilized cyclic monoatomic zero-valent silicon compound (71)

Scheme 25. Synthesis of germylene-stabilized cyclic monoatomic zero-valent silicon compound (77)

Scheme 26. Synthesis of carbene-stabilized diatomic zero-valent silicon compound 79 (a) and 81 (b)

Scheme 27. Synthesis and reactivity of silylene-stabilized diatomic zero-valent silicon compound (83)

Scheme 28. Synthesis of carbene-stabilized monoatomic zero-valent germanium compound 86 (a) and 88 (b)

Scheme 29. Synthesis of pyridine imine-stabilized monoatomic zero-valent germanium compound 90

Scheme 30. Synthesis of carbene-imine ligand stabilized monoatomic zero-valent germanium compound 93

Scheme 31. Synthesis of carbene-stabilized monoatomic zero-valent germanium compound 95 (a) and 96 (b)

Scheme 32. Synthesis of diatomic zero-valent germanium compound 100 (a) and 102 (b)

Scheme 33. Synthesis of imine-stabilized monoatomic zero-valent stannum compound (104)

Scheme 34. Synthesis of silylene-stabilized monoatomic zero-valent stannum compound (106)

Scheme 35. Synthesis and reactivity of germylene-stabilized monoatomic zero-valent stannum compound (109)

Scheme 36. Synthesis of NHC-stabilized dioatomic zero-valent stannum compound (111)

Scheme 37. Synthesis and reactivity of silylene-stabilized diatomic zero-valent stannum compound (113)

Scheme 38. Synthesis of silylene-stabilized monoatomic zero-valent lead compound (118) and (119)

Scheme 39. Synthesis of germylene-stabilized monoatomic zero-valent lead compound (122)

Scheme 40. Reactivity of germylene-stabilized monoatomic zero-valent lead compound (122)

Scheme 41. Synthesis of diphosphene lead π-complex (125)

Scheme 42. Synthesis of carbene-stabilized diatomic zero-valent phosphorus compound 127 (a) and 129 (b)

Scheme 43. Synthesis and reactivity of silylene-stabilized diatomic zero-valent phosphorus compound (130)

Scheme 44. Synthesis (a) and reactivity (b) of NHC-stabilized diatomic zero-valent arsenic compound (135)

Scheme 45. Synthesis of CAAC-stabilized diatomic zero-valent antimony compound (139)

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零价态主族元素化合物的合成、结构与反应性质研究进展^★

Recent Advances in the Synthesis, Structural Characterization, and Reactivity of Zero-Valent Main Group Compounds^★

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零价态主族元素化合物的合成、结构与反应性质研究进展★

Recent Advances in the Synthesis, Structural Characterization, and Reactivity of Zero-Valent Main Group Compounds★

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Fig. & Tab. 45

References 47

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零价态主族元素化合物的合成、结构与反应性质研究进展^★

Recent Advances in the Synthesis, Structural Characterization, and Reactivity of Zero-Valent Main Group Compounds^★