基于含氮配体铝-金属键杂核金属配合物研究进展

doi:10.6023/cjoc202601019

摘要/Abstract

近年来, 含金属-金属键的杂核金属配合物化学逐渐成为金属有机化学的前沿领域之一. 一系列配体稳定的金属-金属键配合物相继被报道, 这类配合物具有独特的电子结构, 并在小分子活化和催化方面展现出特殊的潜力. 开展新型金属-金属键配合物的研究, 对于进一步拓展对化学键的理解和揭示金属之间的协同活化机制具有重要意义. 此文依据该领域的研究进展, 按照合成策略的不同, 对已报道的含氮配体铝-金属键配合物实例进行综述, 着重阐述其合成方法、结构特征以及铝-金属键的反应性质. 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, 杂核金属配合物, 铝配合物, 含氮配体, 反应性

In recent years, the chemistry of heterometallic complexes with metal-metal bonds has become one of the frontier fields in organometallic chemistry. A series of ligand-stabilized complexes featuring metal-metal bonds have been successively reported, which exhibit unique electronic structures and showcase their special potential application in small molecule activation and catalysis. Proceeding with the study of novel metal-metal bonded complexes is of significant importance in further expanding our understanding of the nature of chemical bonds and revealing the mechanisms of heterometallic synergistic effects between different metals. Based on the progress in this aera, the developed heterometallic complexes containing aluminum-metal bonds are reviewed in this paper according to different synthetic strategies. This review mainly elaborates on the efficient strategies to construct heterometallic complexes with aluminum-metal bonds based on nitrogen-containing ligands and also their characteristics and reactivities. Finally, the future developments and applications in this field are also prospected.

Key words: metal-metal bond, heterometallic complex, aluminum complex, nitrogen-containing ligand, reactivity

引用此文

孙雄, 关瑜, 陈浩然. 基于含氮配体铝-金属键杂核金属配合物研究进展[J]. 有机化学, 2026, 46(8): 3025-3052.

Xiong Sun, Yu Guan, Haoran Chen. Research Progress of Heterometallic Complexes with Aluminum-Metal Bonds Based on Nitrogen-Containing Ligands[J]. Chinese Journal of Organic Chemistry, 2026, 46(8): 3025-3052.

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图/表 59

图式1. 配合物2的合成

Scheme 1. Synthesis of complex 2

图式2. 配合物3和4的合成

Scheme 2. Synthesis of complexes 3 and 4

图式3. 配合物5的合成及其反应性

Scheme 3. Synthesis and reactivity of complex 5

图式4. β-二亚胺稳定的Al—M键配合物的合成

Scheme 4. Synthesis of β-diketimine-stabilized Al—M bond complex

图式5. 配合物12的合成

Scheme 5. Synthesis of complex 12

图式6. 配合物14的合成

Scheme 6. Synthesis of complex 14

图式7. 含Al-第一排过渡金属键配合物的合成

Scheme 7. Synthesis of Al-first-row transition metal bond complexes

图式8. 配合物22的合成及其反应性

Scheme 8. Synthesis and reactivity of complex 22

图式9. 配合物29、30和32的合成及其反应性

Scheme 9. Synthesis and reactivity of complexes 29, 30 and 32

图式10. 配合物37和38的合成

Scheme 10. Synthesis of complexes 37 and 38

图式11. 配合物40的合成

Scheme 11. Synthesis of complex 40

图式12. 配合物42的合成

Scheme 12. Synthesis of complex 42

图式13. Al—Fe和Al—Mn键配合物的合成

Scheme 13. Synthesis of complexes with Al—Fe and Al—Mn bond

图式14. 配合物51的合成及其反应性

Scheme 14. Synthesis and reactivity of complex 51

图式15. 配合物51的反应性

Scheme 15. Reactivity of complex 51

图式16. 配合物63的合成及其反应性

Scheme 16. Synthesis and reactivity of complex 63

图式17. Al—Fe键配合物的合成

Scheme 17. Synthesis of complexes containing Al—Fe bonds

图式18. 配合物73的合成

Scheme 18. Synthesis of complex 73

图式19. 配合物74和75的合成及其反应性

Scheme 19. Synthesis and reactivity of complex 74 and 75

图式20. 配合物79的合成及反应性

Scheme 20. Synthesis and reactivity of complex 79

图式21. 配合物81、82和83的合成

Scheme 21. Synthesis of complexes 81, 82 and 83

图式22. 配合物81和82的反应性

Scheme 22. Reactivity of complexes 81 and 82

图式23. 配合物91的合成及反应性

Scheme 23. Synthesis and reactivity of complex 91

图式24. 配合物95的合成

Scheme 24. Synthesis of complex 95

图式25. 配合物98和99的合成及其反应性

Scheme 25. Synthesis and reactivity of complexes 98 and 99

图式26. 配合物102和103的合成及其反应性

Scheme 26. Synthesis and reactivity of complexes 102 and 103

图式27. 含Al-第一族金属配合物的合成及其反应性

Scheme 27. Synthesis and reactivity of Al-group 1 metal complexes

图式28. 配合物119和120的合成及其反应性

Scheme 28. Synthesis and reactivity of complexes 119 and 120

图式29. 配合物126的合成及其反应性

Scheme 29. Synthesis and reactivity of complex 126

图式30. 配合物128的合成及其反应性

Scheme 30. Synthesis and reactivity of complex 128

图式31. 配合物136和137的合成及其反应性

Scheme 31. Synthesis and reactivity of complexes 136 and 137

图式32. 配合物141的合成及其反应性

Scheme 32. Synthesis and reactivity of complex 141

图式33. 配合物149的合成及其反应性

Scheme 33. Synthesis and reactivity of complex 149

图式34. 配合物155的合成及其反应性

Scheme 34. Synthesis and reactivity of complex 155

图式35. 不同类别N-P配体示例

Scheme 35. Examples of different types of N-P ligands

图式36. 配合物163、164和165的合成

Scheme 36. Synthesis of complexes 163, 164 and 165

图式37. 配合物166和167的合成及其反应性

Scheme 37. Synthesis and reactivity of complexes 166 and 167

图式38. 配合物168和169的合成

Scheme 38. Synthesis of complexes 168 and 169

图式39. 配合物170、171和172的合成

Scheme 39. Synthesis of complexes 170, 171 and 172

图式40. 配合物174的合成及其反应性

Scheme 40. Synthesis and reactivity of complex 174

图式41. 配合物183的合成及其反应性

Scheme 41. Synthesis and reactivity of complex 183

图式42. 配合物188的合成及其反应性

Scheme 42. Synthesis and reactivity of complex 188

图式43. 配合物191的合成及其反应性

Scheme 43. Synthesis and reactivity of complex 191

图式44. 配合物194的合成及其反应性

Scheme 44. Synthesis and reactivity of complex 194

图式45. 配合物191的反应性

Scheme 45. Reactivity of complex 191

图式46. 配合物196的合成及其反应性

Scheme 46. Synthesis and reactivity of complex 196

图式47. 配合物200和203的合成及其反应性

Scheme 47. Synthesis and reactivity of complexes 200 and 203

图式48. Al—Rh/Ir键配合物的合成及其反应性

Scheme 48. Synthesis and reactivity of complexes with Al—Rh/Ir bonds

图式49. 配合物216的合成及其反应性

Scheme 49. Synthesis and reactivity of complex 216

图式50. 配合物226的合成及其反应性

Scheme 50. Synthesis and reactivity of complex 226

图式51. 配合物233和234的合成及其反应性

Scheme 51. Synthesis and reactivity of complexes 233 and 234

图式52. 配合物239和240的合成

Scheme 52. Synthesis of complexes 239 and 240

图式53. 配合物241和242的合成及其反应性

Scheme 53. Synthesis and reactivity of complexes 241 and 242

图式54. 配合物244的合成及其反应性

Scheme 54. Synthesis and reactivity of complex 244

图式55. 配合物247和248的合成及其反应性

Scheme 55. Synthesis and reactivity of complexes 247 and 248

图式56. 配合物247和248与杂联烯的反应性

Scheme 56. Reactivity of complexes 247 and 248 with heteroallenes

图式57. 配合物258的合成及其反应性

Scheme 57. Synthesis and reactivity of complex 258

图式58. 配合物258a参与的烯烃C—H键活化

Scheme 58. C—H activation of alkenes with complex 258a

图式59. 配合物258a、267a和267b与小分子的反应性

Scheme 59. Reactivity of complexes 258a, 267a and 267b with small molecules

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