文献类型：期刊文献

中文题名：邻氨基苯硫酚桥联双金属配合物的合成、表征和反应性

英文题名：Synthesis,Characterization and Reactivity of o-Aminobenzenethiolate-Bridged Bimetallic Complexes

作者：陶泽凡[1];王椿焱[1];杨大伟[1];曲景平[1,2]

机构：[1]大连理工大学,精细化工全国重点实验室,教育部智能材料化工前沿科学中心,大连116024;[2]华东理工大学,生物反应器工程全国重点实验室,教育部材料生物学与动态化学前沿科学中心,上海200237

年份：2025

卷号：83

期号：7

起止页码：702

中文期刊名：化学学报

外文期刊名：Acta Chimica Sinica

收录：;WOS:【SCI-EXPANDED(收录号:WOS:001542043700007)】；北大核心:【北大核心2023】；

基金：Project supported by the National Natural Science Foundation of China (Nos. 21690064, 92161204, 92461311, 22471028) .

语种：中文

中文关键词：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

外文关键词：o-aminobenzenethiol;bimetallic complex;heteronuclear complex;synergistic effect;azido complex

摘要：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^(*)=η^(5)-C_(5)Me_(5)),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-η^(2):η^(4)-abt^(R))FeCp^(*)][PF_(6)](2[PF_(6)])、钴钌配合物[Cp^(*)Co(μ-η^(2):η^(6)-abt^(R))RuCp^(*)][PF_(6)](3[PF_(6)])和双钴配合物[Cp^(*)Co(μ-η^(2):η^(2)-abt^(R))(μ-Cl)CoCp^(*)][PF_(6)](4[PF_(6)]).abt^(R)分别以μ-η^(2):η^(4)、μ-η^(2):η^(6)和μ-η^(2):η^(2)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[PF_(6)]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-η^(2):η^(2)-abt)(μ-N_(3))CoCp^(*)][PF_(6)](5[PF_(6)]).不同的是,钴铁配合物2[PF_(6)]和钴钌配合物3[PF_(6)]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.
o-Aminobenzenethiol(abt)and its derivatives(abt^(R)) as a kind of widely used hybrid bidentate ligands have at-tracted 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^(*)=η^(5)-C_(5)Me_(5)) with high selectivity.Furthermore,novel abt^(R)-bridged cobalt-iron complex[Cp^(*)Co(μ-η^(2):η^(4)-abt^(R))FeCp^(*)][PF_(6)](2[PF_(6)]),cobalt-ruthenium complex[Cp^(*)Co(μ-η^(2):η^(6)-abt^(R))RuCp^(*)][PF_(6)](3[PF_(6)])and dicobalt complex[Cp^(*)Co(μ-η^(2):η^(2)-abt^(R))(μ-Cl)CoCp^(*)][PF_(6)](4[PF_(6)])were successfully syn-thesized in high yields,through the assembly reactions between complex 1 and different metal precursors([Cp^(*)Fe(MeCN)3][PF_(6)],[Cp^(*)Ru(MeCN)3][PF_(6)]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-η^(2):η^(4),μ-η^(2):η^(6)andμ-η^(2):η^(2),which are significantly different from the conventional μ-η^(1):η^(2)coordination pattern observed in other reported abt-bridged bimetallic complexes.Owing to the existence of a bridging chloride,complex 4[PF_(6)]can undergo anion ex-change metathesis with sodium azide,yielding dicobalt azido-bridged complex[Cp^(*)Co(μ-η^(2):η^(2)-abt)(μ-N_(3))CoCp^(*)][PF_(6)](5[PF_(6)])in good yield.Crystallographic studies demonstrate that complex 5[PF_(6)]features a bridging azide ligand in a μ1,1-η^(1):η^(1)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[PF_(6)]exhibits good stability whether in photolysis at room temperature or heating at 60℃.Distinctly,under identical reaction conditions,iron-cobalt complex 2[PF_(6)]will decompose into more stable mononuclear cobalt precursor 1,while complex 3[PF_(6)]is inert and does not display any reactivity.Aforementioned research work provides some novel ideas and new methods for the de-sign and development of new-type bioinspired thiolate-bridged bimetallic catalysts.