Synthesis and reactivity of thiolate-bridged multi-iron complexes supported by cyclic (alkyl)(amino)carbene

Zhang Yanpeng; Mei Tao; Yang Dawei; Zhang Yixin; Wang Baomin; Qu Jingping

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Synthesis and reactivity of thiolate-bridged multi-iron complexes supported by cyclic (alkyl)(amino)carbene

机译：环状（烷基）（氨基）卡贝（Amino）Carbene支持的硫醇桥桥多铁络合物的合成与反应性

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The combined utilization of Me-2-cAAC (Me-2-cAAC = : C(CH2)(CMe2)(2)N-2,6-(Pr2C6H3)-Pr-i) and thiolates as supporting ligands enables the access of unprecedented carbene coordinated thiolate-bridged diiron(II) complexes [(Me-2-cAAC)Fe(mu-SR)(Br)](2) (R = Me, 3; R = Et, 4). The coordination environment of each tetrahedral iron(II) center in complexes 3 and 4 is composed of one terminal bromide atom, one carbene carbon atom and two thiolate sulfur atoms, which is similar to the carbide-containing sulfur-rich environment of iron centers in the belt region of the FeMo-cofactor. Interestingly, when NaSCPh3 was chosen as the thiolate ligand, C-S bond homolysis occurred to form a rare [3 : 1] site-differentiated cubane-type cluster [(Me-2-cAAC)Fe4S4(Br)(3)][Me-2-cAACH] (5). Furthermore, complexes 3 and 4 exhibit good exchange reactivity toward the azide anion to give novel thiolate-bridged diiron complexes with two azido ligands in a trans arrangement.

机译：作为支撑配体的ME-2-CAAC（ME-2-CAAC =：C（CH2）（CME2）（2）N-2,6-（PR2C6H3）-PR-I）和硫醇酸盐的合并利用使得能够获得前所未有的卡贝丁配位硫醇纤维桥（II）配合物[（ME-2-CAAC）Fe（MU-SR）（BR）]（2）（R = ME，3; R = ET，4）。复合物3和4中的每种四面体铁（II）中心的配位环境由一个末端溴化物，一种碳氮碳原子和两个硫醇硫原子组成，其类似于含有碳化物富含铁的铁心环境股骨辅因子的皮带区域。 Interestingly, when NaSCPh3 was chosen as the thiolate ligand, CS bond homolysis occurred to form a rare [3 : 1] site-differentiated cubane-type cluster [(Me-2-cAAC)Fe4S4(Br)(3)][Me- 2-caach]（5）。此外，复合物3和4对叠氮化阴离子表现出良好的交换反应性，以使新的硫醇晶体桥型Dions络合物与反式排列中的两种氮杂物配体。

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《Dalton transactions: An international journal of inorganic chemistry》 |2017年第45期|共9页
作者
Zhang Yanpeng; Mei Tao; Yang Dawei; Zhang Yixin; Wang Baomin; Qu Jingping;
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Dalian Univ Technol State Key Lab Fine Chem Dalian 116024 Peoples R China;

Dalian Univ Technol State Key Lab Fine Chem Dalian 116024 Peoples R China;

Dalian Univ Technol State Key Lab Fine Chem Dalian 116024 Peoples R China;

Dalian Univ Technol State Key Lab Fine Chem Dalian 116024 Peoples R China;

Dalian Univ Technol State Key Lab Fine Chem Dalian 116024 Peoples R China;

Dalian Univ Technol State Key Lab Fine Chem Dalian 116024 Peoples R China;

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正文语种 eng
中图分类化学;无机化学;
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1. Synthesis and reactivity of thiolate-bridged multi-iron complexes supported by cyclic (alkyl)(amino)carbene [J] . Zhang Yanpeng, Mei Tao, Yang Dawei, Dalton transactions: An international journal of inorganic chemistry . 2017,第45期

机译：环状（烷基）（氨基）卡贝（Amino）Carbene支持的硫醇桥桥多铁络合物的合成与反应性
2. Synthesis, structure and DFT calculations of mononuclear cyclic (alkyl)(amino) carbene supported titanium(II) complexes [J] . Ma Wangyang, Zhang Jing-Xuan, Lin Zhenyang, Dalton transactions: An international journal of inorganic chemistry . 2019,第40期

机译：单核环循环（烷基）（氨基）卡苯磺酸钛（II）复合物的合成，结构和DFT计算
3. Synthesis, structure and cytotoxicity of cyclic (alkyl)(amino) carbene and acyclic carbene complexes of group 11 metals [J] . Bertrand Benoit, Romanov Alexander S., Brooks Mark, Dalton transactions: An international journal of inorganic chemistry . 2017,第45期

机译：环状（烷基）（氨基）卡宾和11族金属环纤维络合物的合成，结构和细胞毒性
4. Gas Phase Synthesis, Characterization, and Reactivity of Gold (I) Carbene Complexes [C] . Christopher Swift, Scott Gronert ASMS Conference on Mass Spectrometry and Allied Topics . 2014

机译：金（I）卡宾配合物的气相合成，表征和反应性
5. Reactivity of bis(amino)cyclopropenylidenes (BACs) and cyclic (alkyl)(amino)carbenes (CAACs): Coordination chemistry, catalysis, and small molecule activation. [D] . Kuchenbeiser, Glenn Richard. 2009

机译：双（氨基）环丙烯基（BAC）和环状（烷基）（氨基）卡宾（CAAC）的反应性：配位化学，催化和小分子活化。
6. Reactivity of Cyclic (Alkyl)(amino)carbenes (CAACs) and Bis(amino)cyclopropenylidenes (BACs) with Heteroallenes: Comparisons with their N-heterocyclic Carbene (NHCs) Counterparts [O] . Glenn Kuchenbeiser, Michele Soleilhavoup, Bruno Donnadieu, -1

机译：环状（烷基）（氨基）碳酸盐（CAAC）和双（氨基）环烯酮（BAC）与杂丙烯的反应性：与其正杂环（NHCS）对应物的比较
7. Synthesis, structure and cytotoxicity of cyclic (alkyl)(amino) carbene and acyclic carbene complexes of group 11 metals [O] . Benoît Bertrand, Alexander S. Romanov, Mark Brooks, 2017

机译：环状（烷基）（氨基）卡宾和11族金属环纤维络合物的合成，结构和细胞毒性

Synthesis and reactivity of thiolate-bridged multi-iron complexes supported by cyclic (alkyl)(amino)carbene

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