Synthesis, Characterization and Reactivity of o-Aminobenzenethiolate-Bridged Bimetallic Complexes

doi:10.6023/A25050162

Abstract

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

Cite this article

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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Fig. & Tab. 9

Figure 1. Representative examples of abtR-bridged bimetallic complexes

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]

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)

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

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)

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

Figure 5. Synthesis of complex 5[PF6]

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)

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

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