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首页> 外文期刊>Dalton transactions: An international journal of inorganic chemistry >Binuclear nickel complexes with an edge sharing bis(square-pyramidal) N_3Ni(μ-S_2)NiN_3 core: Synthesis, characterization, crystal structure and magnetic properties
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Binuclear nickel complexes with an edge sharing bis(square-pyramidal) N_3Ni(μ-S_2)NiN_3 core: Synthesis, characterization, crystal structure and magnetic properties

机译：边缘共享双（方形锥体）N_3Ni（μ-S_2）NiN_3核的双核镍配合物：合成，表征，晶体结构和磁性

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The synthesis of the novel macrocyclic octadentate amino-thiophenolate ligand H_2L2 (3,7,11,19,23,27-hexaaza-33,34-dithiol-15,31-di(tert- butyl)-tricyclo[27,3,1~(13.17)]-tetratriaconta-1(32),13,15,17(34),29,30- hexane) and its ability to support binuclear nickel(ii) complexes with dithiolato-bridged square-pyramidal Ni~(II) ions are reported. H_2L2 is obtained as the hexahydrobromide salt from a Schiff-base condensation reaction between 1,2-bis(4-tert-butyl-2,6-diformylphenylthio)ethane and bis(3-aminopropyl)amine followed by two successive reductions with NaBH4 and Na/NH3. The ligand forms a green, paramagnetic, binuclear nickel(ii) complex dication [Ni~(II)_2L2]~(2+), which can be isolated as a ClO_4 - (4) or BPh_4 - salt (5). The binuclear nickel(ii) complex contains a central N_3Ni(μ-S)_2NiN_3 core with two square-pyramidal coordinated NiII ions. The [Ni_2L2]~(2+) dication does not bind further coligands, in striking contrast to the behaviour of the parent [Ni_2L1]~(2+) dication supported by the smaller (L1)2- macrocycle (containing diethylenetriamine in place of the dipropylenetriamine units) which readily binds a variety of other coligands (L′) to form bisoctahedral [Ni_2L1(L′)]~+ structures. The unusual behaviour of 4 relates to two different N configurations which leads to a steric shielding of the third bridging position by the CH_2-groups of the dipropylenetriamine chains. An analysis of the temperature-dependent magnetic susceptibility data of 5 reveals the presence of a weak antiferromagnetic exchange interaction between the spins of the nickel(ii) ions with a value for the magnetic exchange coupling constant J of -23.5 cm~(-1) (H = -2JS_1S_2). These results are further substantiated by DFT calculations.
机译：新型大环八齿氨基硫酚酸酯配体H_2L2（3,7,11,19,23,27-六氮杂-33,34-二硫醇-15,31-二（叔丁基）-三环[27,3， 1〜（13.17）]-tetratriaconta-1（32），13,15,17（34），29,30-己烷）及其通过双硫醇桥联的方形金字塔形Ni〜（2）支撑双核镍（ii）配合物的能力。 II）报道了离子。 H_2L2是六氢溴酸盐，由1,2-双（4-叔丁基-2,6-二甲酰基苯硫基）乙烷与双（3-氨基丙基）胺之间的席夫碱缩合反应制得，然后依次用NaBH4和Na / NH3配体形成绿色，顺磁性，双核镍（ii）复合指示[Ni〜（II）_2L2]〜（2+），可以分离为ClO_4-（4）或BPh_4-盐（5）。双核镍（ii）配合物包含一个中心N_3Ni（μ-S）_2NiN_3核，该核具有两个方形金字塔形配位的NiII离子。 [Ni_2L2]〜（2+）指示剂不与其他大肠菌素结合，这与较小的（L1）2-大环（含二亚乙基三胺代替）支持的母体[Ni_2L1]〜（2+）指示剂的行为形成鲜明对比。 （二丙烯三胺单元），可以很容易地与多种其他大分子配体（L'）结合形成双八面体[Ni_2L1（L'）]〜+结构。 4的异常行为与两个不同的N构型有关，这导致通过二亚丙基三胺链的CH_2-基对第三桥接位置进行空间屏蔽。对5随温度变化的磁化率数据的分析表明，镍（ii）离子的自旋之间存在弱的反铁磁交换相互作用，其磁交换耦合常数J值为-23.5 cm〜（-1） （H = -2JS_1S_2）。 DFT计算进一步证实了这些结果。

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