邻氨基苯硫酚桥联双金属配合物的合成、表征和反应性

doi:10.6023/A25050162

摘要/Abstract

邻氨基苯硫酚(abt)及其衍生物(abt^R)是一种应用广泛的混合型双齿配体, 但因其复杂的氧化还原活性导致定向构筑邻氨基苯硫酚桥联双金属配合物极具挑战性. 本研究以abt^R为配体, 设计合成了一种新型单钴配合物[Cp*Co(abt^R)] (1, Cp*=η⁵-C₅Me₅), 进一步采用不同前体间的组装策略, 分别与单核铁、单核钌和双核钴配合物前体进行反应, 高选择性地构筑了abt^R桥联钴铁配合物[Cp*Co(μ-η²:η⁴-abt^R)FeCp*][PF₆] (2[PF₆])、钴钌配合物[Cp*Co(μ-η²:η⁶-abt^R)RuCp*][PF₆] (3[PF₆])和双钴配合物[Cp*Co(μ-η²:η²-abt^R)(μ-Cl)CoCp*][PF₆] (4[PF₆]). abt^R分别以μ-η²:η⁴、μ-η²:η⁶和μ-η²:η²三种不同的配位方式桥联于双金属中心. 其中, 双钴配合物4[PF₆]能够与叠氮钠发生配体交换反应, 生成稳定的双钴叠氮桥联配合物[Cp*Co(μ-η²:η²-abt)(μ-N₃)CoCp*][PF₆] (5[PF₆]). 不同的是, 钴铁配合物2[PF₆]和钴钌配合物3[PF₆]并不具备类似的反应性能. 该研究工作为新型双金属协同催化剂的设计开发提供了新方法与新思路.

关键词: 邻氨基苯硫酚, 双金属配合物, 异核配合物, 协同作用, 叠氮配合物

o-Aminobenzenethiol (abt) and its derivatives (abt^R) as a kind of widely used hybrid bidentate ligands have attracted extensive attention, however, it is highly challenging for the oriented construction of abt-bridged bimetallic complexes due to their complicated redox activity. This paper presents the synthesis and characterization of three kinds of abt-bridged bimetallic complexes and their reactivity toward sodium azide. Using abt^R as auxiliary ligands, we successfully synthesized a new-type of mononuclear cobalt complex [Cp*Co(abt^R)] (1, Cp*=η⁵-C₅Me₅) with high selectivity. Furthermore, novel abt^R-bridged cobalt-iron complex [Cp*Co(μ-η²:η⁴-abt^R)FeCp*][PF₆] (2[PF₆]), cobalt-ruthenium complex [Cp*Co(μ-η²:η⁶-abt^R)RuCp*][PF₆] (3[PF₆]) and dicobalt complex [Cp*Co(μ-η²:η²-abt^R)(μ-Cl)CoCp*][PF₆] (4[PF₆]) were successfully synthesized in high yields, through the assembly reactions between complex 1 and different metal precursors ([Cp*Fe(MeCN)₃][PF₆], [Cp*Ru(MeCN)₃][PF₆] or dimer [Cp*Co(μ-Cl)₂(t-Cl)₂CoCp*]). Single-crystal X-ray diffraction analysis indicates that the abt^R ligand is coordinated to the bimetallic centers in three different ways: μ-η²:η⁴, μ-η²:η⁶ and μ-η²:η², which are significantly different from the conventional μ-η¹:η² coordination pattern observed in other reported abt-bridged bimetallic complexes. Owing to the existence of a bridging chloride, complex 4[PF₆] can undergo anion exchange metathesis with sodium azide, yielding dicobalt azido-bridged complex [Cp*Co(μ-η²:η²-abt)(μ-N₃)CoCp*][PF₆] (5[PF₆]) in good yield. Crystallographic studies demonstrate that complex 5[PF₆] features a bridging azide ligand in a μ_1,1-η¹:η¹ coordination mode, with a remarkably short Co—Co distance of 0.2751(1) nm and a slightly bent N=N=N bond angle of 168(1)°. Unlike our previously reported dicobalt azide complexes, the bridging azido group in 5[PF₆] exhibits good stability whether in photolysis at room temperature or heating at 60 ℃. Distinctly, under identical reaction conditions, iron-cobalt complex 2[PF₆] will decompose into more stable mononuclear cobalt precursor 1, while complex 3[PF₆] is inert and does not display any reactivity. Aforementioned research work provides some novel ideas and new methods for the design and development of new-type bioinspired thiolate-bridged bimetallic catalysts.

Key words: o-aminobenzenethiol, bimetallic complex, heteronuclear complex, synergistic effect, azido complex

引用此文

陶泽凡, 王椿焱, 杨大伟, 曲景平. 邻氨基苯硫酚桥联双金属配合物的合成、表征和反应性[J]. 化学学报, 2025, 83(7): 702-708.

Zefan Tao, Chunyan Wang, Dawei Yang, Jingping Qu. Synthesis, Characterization and Reactivity of o-Aminobenzenethiolate-Bridged Bimetallic Complexes[J]. Acta Chimica Sinica, 2025, 83(7): 702-708.

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图/表 9

图1. 代表性的邻氨基苯硫酚桥联双金属配合物

Figure 1. Representative examples of abtR-bridged bimetallic complexes

图2. 配合物2[PF6]、3[PF6]和4[PF6]的合成a

Figure 2. Synthesis of complexes 2[PF6], 3[PF6] and 4[PF6]a a Reaction conditions: (i) 1 equiv. [Cp*Fe(MeCN)3][PF6], CH2Cl2, －78 ℃ to r.t., 91% for 2a[PF6] and 92% for 2b[PF6]; (ii) 1 equiv. [Cp*Ru(MeCN)3]- [PF6], CH2Cl2, －78 ℃ to r.t., 98% for 3a[PF6] and 95% for 3b[PF6]; (iii) 1 equiv. [Cp*Co(μ-Cl)2(t-Cl)2CoCp*], 1 equiv. KPF6, MeOH, －78 ℃ to r.t., 82% for 4a[PF6] and 94% for 4b[PF6]

图3. 配合物2a[PF6](上)和3a[BPh4](下)的分子结构(椭球率为30%, 碳原子上的氢原子和抗负离子或已省略)

Figure 3. Molecular structures of complexes 2a[PF6] (top) and 3a[BPh4] (bottom) (Thermal ellipsoids are shown at a 30% probability level. Hydrogen atoms on carbons and counter anion or are omitted for clarity)

	2a[PF₆]	2b[PF₆]	3a[BPh₄]	3b[BPh₄]
	距离/nm
Co…Fe	0.25925(9)	0.26156(6)	—	—
Co—N	0.1872(5)	0.1903(2)	0.1858(3)	0.1757(8)
Co—S	0.2157(2)	0.21589(8)	0.2157(1)	0.2191(3)
Co—Cp*	0.16693(7)	0.16807(5)	0.16485(4)	0.16763(7)
Fe/Ru—Cp*	0.16869(7)	0.16921(6)	0.18099(4)	0.18011(5)
	二面角/(°)
Cp1∠Cp2	59.9(3)	56.8(1)	87.6(2)	87.8(6)

表1. 配合物2[PF6]和3[BPh4]的主要结构数据

Table 1. Main structural data of complexes 2[PF6] and 3[BPh4]

图4. 配合物4a[BPh4](上)和4b[BPh4](下)的分子结构(椭球率为30%, 碳原子上的氢原子和抗负离子已省略)

Figure 4. Molecular structures of complexes 4a[BPh4] (top) and 4b[BPh4] (bottom) (Thermal ellipsoids are shown at a 30% probability level. Hydrogen atoms on carbons and counter anion are omitted for clarity)

	4a[BPh₄]	4b[BPh₄]
	距离/nm
Co…Co	0.27839(7)	0.2805(1)
Co—N	0.1992(3)	0.204(1)
Co—S	0.2298(1)	0.2277(6)
Co—Cl	0.2337(1)	0.2276(2)
Co—Cp*	0.16769(3)	0.16875(6)
	二面角/(°)
Cp1∠Cp2	6.0(3)	1.9(3)

表2. 配合物4a[BPh4]和4b[BPh4]的主要结构数据

Table 2. Main structural data of complexes 4a[BPh4] and 4b[BPh4]

图5. 配合物5[PF6]的合成

Figure 5. Synthesis of complex 5[PF6]

图6. 配合物5[PF6]的分子结构(椭球率为30%, 碳原子上的氢原子和抗负离子已省略)

Figure 6. Molecular structure of complex 5[PF6] (Thermal ellipsoids are shown at a 30% probability level. Hydrogen atoms on carbons and counter anion are omitted for clarity)

图7. 配合物5[PF6]的紫外-可见吸收光谱

Figure 7. UV-vis spectrum of complex 5[PF6]

参考文献 34

[1]	(a) Jasniewski A. J.; Lee C. C.; Ribbe M. W.; Hu Y. Chem. Rev. 2020, 120, 5107. doi: 10.1021/acs.chemrev.9b00704 pmid: 32129988
	(b) Lubitz W.; Ogata H.; Rudiger O.; Reijerse E. Chem. Rev. 2014, 114, 4081. pmid: 32129988
[2]	Buchwalter P.; Rose J.; Braunstein P. Chem. Rev. 2015, 115, 28. doi: 10.1021/cr500208k pmid: 25545815
[3]	Sproules S.; Wieghardt K. Coord. Chem. Rev. 2010, 254, 1358.
[4]	Zhou S.; Yu C.; Chen M.; Shi C.; Gu R.; Qu D. Smart Mol. 2023, 1, e20220009.
[5]	Das A.; Han Z.; Brennessel W. W.; Holland P. L.; Eisenberg R. ACS Catal. 2015, 5, 1397.
[6]	Gordon J. B.; Mcgale J. P.; Prendergast J. R.; Shirani S. Z.; Siegler M. A.; Jameson G. N. L.; Goldberg D. P. J. Am. Chem. Soc. 2018, 140, 14807. doi: 10.1021/jacs.8b08349 pmid: 30346746
[7]	Fiedler A. T.; Lindeman S. V.; Fishcer A. A. Chem. Commun. 2018, 54, 11344.
[8]	Cimadevilla F.; Garcia M. E.; Garcia-Vivo D.; Ruiz M. A.; Graiff C.; Tiripicchio A. Inorg. Chem. 2012, 51, 7284. doi: 10.1021/ic300626y pmid: 22715993
[9]	(a) Zhang J.; Ma L.; Cai R.; Weng L.; Zhou X. Organometallics 2005, 24, 738.
	(b) Mandal S.; Samanta S.; Mondal T.; Goswami S. Organometallics 2012, 31, 5282.
[10]	(a) Chen Y.; Zhou Y.; Chen P.; Tao Y.; Li Y.; Qu J. J. Am. Chem. Soc. 2008, 130, 15250.
	((b) Li S.; Ouyang Z.; Zou J.; Wang D.; Xu B.; Deng L. Acta Chim. Sinica 2022, 80, 272 (in Chinese).
	(李尚钊, 欧阳振武, 邹俊杰, 王东阳, 许斌, 邓亮, 化学学报, 2022, 80, 272.) doi: 10.6023/A22010038
[11]	Chen Y.; Liu L.; Peng Y.; Chen P.; Luo Y.; Qu J. J. Am. Chem. Soc. 2011, 133, 1147.
[12]	Li Y.; Li Y.; Wang B.; Luo Y.; Yang D.; Tong P.; Zhao J.; Luo L.; Zhou Y.; Chen S.; Cheng F.; Qu J. Nat. Chem. 2013, 5, 320. doi: 10.1038/nchem.1594 pmid: 23511421
[13]	Zhang Y.; Zhao J.; Yang D.; Wang B.; Zhou Y.; Wang J.; Chen H.; Mei T.; Ye S.; Qu J. Nat. Chem. 2022, 14, 46.
[14]	Yang D. Wang B.; Qu J. Acc. Chem. Res. 2024, 57, 1761.
[15]	Tong P.; Xie W.; Yang D.; Wang B.; Ji X.; Li J.; Qu J. Dalton Trans. 2016, 45, 18559.
[16]	Koelle U.; Fuss B.; Belting M.; Raabe E. Organometallics 1986, 5, 980.
[17]	Miller E. J.; Landon S. J.; Brill T. B. Organometallics 1985, 4, 533.
[18]	(a) Su L.; Yang D.; Jiang Y.; Li Y.; Di K.; Wang B.; Ye S.; Qu J. Angew. Chem. Int. Ed. 2022, 61, e202203121.
	(b) Guo C.; Su L.; Yang D.; Wang B.; Qu J. Chin. Chem. Lett. 2022, 33, 217.
[19]	Bentley K.; Hareram M. D.; Wang G.; Millman A. A. V.; Perez O. I.; Nichols L. M.; Bories C. C.; Walker L. E.; Woodward A. W.; Golovanov A. P.; Natrajan L. S.; Larrosa I. J. Am. Chem. Soc. 2025, 147, 5035. doi: 10.1021/jacs.4c14835 pmid: 39901642
[20]	Sun B.; Yoshino T.; Matsunaga S.; Kanai M. Adv. Synth. Catal. 2014, 356, 1491.
[21]	Yang D.; Li Y.; Wang B.; Zhao X.; Su L.; Chen S.; Tong P.; Luo Y.; Qu J. Inorg. Chem. 2015, 54, 10243.
[22]	Mori S.; Mochida T. Organometallics 2013, 32, 283.
[23]	Chen Y.; Huang D.; Shi X.; Xi Z.; Wei J. Acta Chim. Sinica 2024, 82, 471 (in Chinese).
	(陈元金, 黄大江, 石向辉, 席振峰, 魏俊年, 化学学报, 2024, 82, 471.)
[24]	Banerjee A.; Banerjee S.; Garcia G. C. J.; Benmansour S.; Chattopadhyay S. ACS Omega 2019, 4, 20634. doi: 10.1021/acsomega.9b02764 pmid: 31858049
[25]	Stackpole B. J.; Fredericksen J. M.; Brasch N. E. J. Inorg. Biochem. 2024, 254, 112504.
[26]	Seengupta D.; Sandoval P. C.; Schueller E.; Encerrado M. A. M.; Metta M. A.; Lee W.; Seshadri R.; Pinter B.; Fortier S. J. Am. Chem. Soc. 2020, 142, 8233.
[27]	Zhang Y.; Tong P.; Yang D.; Li J.; Wang B.; Qu J. Chem. Commun. 2017, 53, 9854.
[28]	Mei T.; Zhang P.; Song Z.; Wang B.; Qu J.; Ye S.; Yang D. J. Am. Chem. Soc. 2023, 145, 20578.
[29]	(a) Ray A.; Rosair G. M.; Pilet G.; Dede B.; Gomez C. J.; Signorella S.; Bellu S.; Mitra S. Inorg. Chim. Acta 2011, 375, 20.
	(b) Sommer M, G.; Marx R.; Schweinfurth D.; Rechkemmer Y.; Neugebauer P.; Meer M.; Hohloch S.; Demeshko S.; Meyer F.; Slageren J. V.; Sarlar B. Inorg. Chem. 2017, 56, 402.
[30]	(a) Wang L.; Zhao B.; Zhang C.; Liao D.; Jiang Z.; Yan S. Inorg. Chem. 2003, 42, 5804. pmid: 12971747
	(b) Jana A.; Konar S.; Das K.; Ray S.; Golen J. A.; Rheingold A. L.; Carrella L. M.; Rentschler E.; Mondal T. K.; Kar S. K. Polyhedron 2012, 38, 258. pmid: 12971747
	(c) Makino M.; Ishizuka T.; Ohzu S.; Hua J.; Kotani H.; Kojima T. Inorg. Chem. 2013, 52, 5507. pmid: 12971747
[31]	Vreeken V.; Siegler M. A.; Bruin B.; Reek J. N. H.; Lutz M.; Vlugt J. I. Angew. Chem. Int. Ed. 2015, 54, 7055.
[32]	Catheline D.; Astruc D. Organometallics 1984, 3, 1094.
[33]	Fagan P. J.; Ward M. D.; Calabrese J. C. J. Am. Chem. Soc. 1989, 111, 1698.
[34]	Delgado S.; Macazaga J.; Moreno C.; Masaguer J. R. J. Organomet. Chem. 1985, 289, 397.