Flash Communication: Synthesis of Nickel-Lanthanide Sulfido-bridged Coordination Clusters Using an Acid–Base Interaction

IF 2.4 3区化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR

Organometallics Pub Date : 2026-10-12 Epub Date: 2026-09-23 DOI:10.1021/acs.organomet.6c00280

Anastasiia Yu. Konokhova, Mikhail Yu. Afonin, Kristina A. Aidakova, Artem S. Bogomyakov, Artem G. Demkin, Taisiya S. Sukhikh, Nikolay B. Kompankov, Sergey N. Konchenko

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引用次数: 0

Abstract

The reactions between [Cp*₂Ln(allyl)] and [(dppe)Ni(SH)₂] (dppe = Ph₂PCH₂CH₂PPh₂) or [(POCOP^iPr)Ni(SH)] (POCOP^iPr = C₆H₃(OP(ⁱPr)₂)₂) proceed as a classic acid–base interaction in which the nickel hydrosulfide complexes serve as typical Brønsted acids. In case of the dibasic acid [(dppe)Ni(SH)₂] the reactions lead to tetrametal coordination clusters [{(dppe)Ni}₂(μ₃-S)₄{LnCp*}₂] (Ln = Dy (1), Ho (2)) and accompanied by elimination of propene and Cp*H, while in case of monobasic acid [(POCOP^iPr)Ni(SH)] only (allyl)⁻ serves as a proton acceptor and the reactions result in formation of bimetal species [(POCOP^iPr)Ni(μ-S){LnCp*₂}] (Ln = Dy (3), Ho (4), Y (5)). Single-crystal X-ray diffraction (XRD) revealed correspondingly tetrametal and dimetal sulfido-bridged Ni/S/Ln frameworks, with the binuclear complexes exhibiting exceptionally short Ln–S bond distances. Magnetic measurements of the Ni/Dy and Ni/Ho complexes showed that the Ni(II) centers are diamagnetic and that the magnetic behavior is governed by corresponding lanthanide ion(s). For 3 field-induced slow magnetic relaxation was observed, with an effective relaxation barrier of 22 K.

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闪光通讯：利用酸碱相互作用合成镍-镧系硫化物桥接配簇

[Cp*2Ln（烯丙基）]与[(dppe)Ni(SH)2] （dppe = Ph2PCH2CH2PPh2）或[(POCOPiPr)Ni(SH)]（POCOPiPr =C6H3(OP(iPr)2)2）之间的反应是典型的酸碱相互作用，其中氢硫化镍配合物作为典型的br ø nsted酸。在二元酸[(dppe)Ni(SH)2]反应中，生成四金属配位簇[{(dppe)Ni}2(μ3-S)4{LnCp*}2] (Ln= Dy (1), Ho(2))，并伴有丙烯和Cp*H的消除，而在单基酸[(POCOPiPr)Ni(SH)]中，只有（烯丙基）−作为质子受体，反应生成双金属[(POCOPiPr)Ni(μ-S){LnCp*2}] (Ln= Dy (3), Ho （4)， Y(5)）。单晶x射线衍射（XRD）显示相应的四金属和双金属硫桥接Ni/S/Ln框架，双核配合物显示出异常短的Ln - S键距离。Ni/Dy和Ni/Ho配合物的磁性测量表明，Ni（II）中心具有抗磁性，其磁性行为受相应的镧系离子控制。对3种磁场诱导的慢磁弛豫进行了观察，有效弛豫势垒为22K。

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来源期刊

Organometallics 化学-无机化学与核化学

CiteScore

5.60

自引率

7.10%

发文量

382

审稿时长

1.7 months

期刊介绍： Organometallics is the flagship journal of organometallic chemistry and records progress in one of the most active fields of science, bridging organic and inorganic chemistry. The journal publishes Articles, Communications, Reviews, and Tutorials (instructional overviews) that depict research on the synthesis, structure, bonding, chemical reactivity, and reaction mechanisms for a variety of applications, including catalyst design and catalytic processes; main-group, transition-metal, and lanthanide and actinide metal chemistry; synthetic aspects of polymer science and materials science; and bioorganometallic chemistry.