Fomenko Iakov S, Afewerki Medhanie, Gongola Marko I, Vasilyev Eugene S, Shul'pina Lidia S, Ikonnikov Nikolay S, Shul'pin Georgiy B, Samsonenko Denis G, Yanshole Vadim V, Nadolinny Vladimir A, Lavrov Alexander N, Tkachev Alexey V, Gushchin Artem L
Nikolaev Institute of Inorganic Chemistry, Siberian Branch of Russian Academy of Sciences, 3 Acad. Lavrentiev Ave., 630090 Novosibirsk, Russia.
Department of Natural Sciences, Novosibirsk State University, 1 Pirogova Str., 630090 Novosibirsk, Russia.
Molecules. 2022 Jun 24;27(13):4072. doi: 10.3390/molecules27134072.
The reactions of CuX (X = Cl, Br) with dipinodiazafluorenes yielded four new complexes [CuXL] (X = Cl (), Br (), L = (1R,3R,8R,10R)-2,2,9,9-Tetramethyl-3,4,7,8,9,10-hexahydro-1H-1,3:8,10-dimethanocyclopenta [1,2-b:5,4-b']diquinolin-12(2H)-one) and [(CuX)L]n (X = Cl (), Br (), L = (1R,3R,8R,10R,1'R,3'R,8'R,10'R)-2,2,2',2',9,9,9',9'-Octamethyl-1,1',2,2',3,3',4,4',7,7',8,8',9,9',10,10'-hexadecahydro-1,3:1',3':8,10:8',10'-tetramethano-12,12'-bi(cyclopenta [1,2-b:5,4-b']diquinolinylidene). The complexes were characterized by IR and EPR spectroscopy, HR-ESI-MS and elemental analysis. The crystal structures of compounds , and were determined by X-ray diffraction (XRD) analysis. Complexes - have a monomeric structure, while complex has a polymeric structure due to additional coordinating N,N sites in L. All complexes contain a binuclear fragment {Cu(μ-X)} (X = Cl, Br) in their structures. Each copper atom has a distorted square-pyramidal coordination environment formed by two nitrogen atoms and three halogen atoms. The Cu-N distance is elongated compared to Cu-N. The EPR spectra of compounds - in CHCN confirm their paramagnetic nature due to the d electronic configuration of the copper(II) ion. The magnetic properties of all compounds were studied by the method of static magnetic susceptibility. For complexes and , the effective magnetic moments are ≈ 1.87 and 1.83 (per each Cu ion), respectively, in the temperature range 50-300 K, which are close to the theoretical spin value (1.73 ). Ferromagnetic exchange interactions between Cu(II) ions inside {Cu(μ-X)X} (X = Cl, Br) dimers (/ ≈ 25 and 31 K for and , respectively) or between dimers (' ≈ 0.30 and 0.47 K for and , respectively) were found at low temperatures. For compounds and , the magnetic susceptibility is well described by the Curie-Weiss law in the temperature range 1.77-300 K with ≈ 1.72 and 1.70 for and , respectively, and weak antiferromagnetic interactions ≈ -0.4 K for and -0.65 K for ). Complexes - exhibit high catalytic activity in the oxidation of alkanes and alcohols with peroxides. The maximum yield of cyclohexane oxidation products reached 50% (complex ). Based on the data on the study of regio- and bond-selectivity, it was concluded that hydroxyl radicals play a decisive role in the oxidation reaction. The initial products in reactions with alkanes are alkyl hydroperoxides.
CuX（X = Cl，Br）与联苯二氮芴反应生成了四种新的配合物[CuXL]（X = Cl（），Br（），L =（1R，3R，8R，10R）-2,2,9,9-四甲基-3,4,7,8,9,10-六氢-1H-1,3:8,10-二亚甲基环戊并[1,2-b:5,4-b']二喹啉-12（2H）-酮）和[(CuX)L]n（X = Cl（），Br（），L =（1R，3R，8R，10R，1'R，3'R，8'R，10'R）-2,2,2',2',9,9,9',9'-八甲基-1,1',2,2',3,3',4,4',7,7',8,8',9,9',10,10'-十六氢-1,3:1',3':8,10:8',10'-四亚甲基-12,12'-联（环戊并[1,2-b:5,4-b']二喹啉亚基）。通过红外光谱和电子顺磁共振光谱、高分辨电喷雾电离质谱和元素分析对这些配合物进行了表征。通过X射线衍射（XRD）分析确定了化合物、和的晶体结构。配合物 - 具有单体结构，而配合物由于L中额外的配位N，N位点而具有聚合结构。所有配合物在其结构中都含有双核片段{Cu(μ-X)}（X = Cl，Br）。每个铜原子都有一个由两个氮原子和三个卤素原子形成的扭曲的四方锥配位环境。与Cu-N相比，Cu-N距离拉长。化合物 - 在CHCN中的电子顺磁共振光谱证实了由于铜（II）离子的d电子构型它们具有顺磁性。通过静态磁化率方法研究了所有化合物的磁性。对于配合物和，在50 - 300 K的温度范围内，有效磁矩分别约为1.87和1.83 （每个Cu离子），这与理论自旋值（1.73 ）接近。在低温下发现{Cu(μ-X)X}（X = Cl，Br）二聚体内部的Cu（II）离子之间（对于和分别为/≈25和31 K）或二聚体之间（对于和分别为'≈0.30和0.47 K）存在铁磁交换相互作用。对于化合物和，在1.77 - 300 K的温度范围内，磁化率可以很好地用居里 - 外斯定律描述，对于和分别为≈1.72和1.70 ，并且存在弱反铁磁相互作用（对于为≈ - 0.4 K，对于为 - 0.65 K）。配合物 - 在过氧化物存在下对烷烃和醇的氧化反应中表现出高催化活性。环己烷氧化产物的最大产率达到50%（配合物）。基于区域和键选择性研究的数据，得出结论：羟基自由基在氧化反应中起决定性作用。与烷烃反应的初始产物是烷基过氧化氢。
