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首页> 外文期刊>Inorganic Chemistry: A Research Journal that Includes Bioinorganic, Catalytic, Organometallic, Solid-State, and Synthetic Chemistry and Reaction Dynamics >Design and synthesis of a new binucleating ligand via cobalt-promoted C-N bond fusion reaction. Ligand isolation and its coordination to nickel, palladium, and platinum
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Design and synthesis of a new binucleating ligand via cobalt-promoted C-N bond fusion reaction. Ligand isolation and its coordination to nickel, palladium, and platinum

机译：通过钴促进的C-N键融合反应设计和合成新的双核配体。配体隔离及其与镍，钯和铂的配位

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A new polydentate bridging ligand, NH4C5N=NC6H4N(H)C5H4N (HL2), is synthesized by the cobalt-mediated phenyl ring amination of coordinated NH4C5N=NC6H5. The green cobalt complex intermediate [Co(L-2)(2)](ClO4), [1](ClO4), and the free ligand HL2 were isolated and characterized. The X-ray structure of [H2L2] (ClO4) is reported. The ligand, upon deprotonation, behaves as a bridging ligand. It reacts with NiCl2-6H(2)O and Na-2[PdCl4] to produce dimetallic complexes, [Ni2Cl2(L-2)(2)], 2, and [Pd-2(L-2)(2)](ClO4)(2), [3](ClO4)(2), respectively. X-ray structures of these two dimetallic complexes are reported. The structure of the dinickel complex, in particular, is unique. In this complex, the two deprotonated secondary amine nitrogens of the two [L2](-) igands bind to two nickel centers simultaneously forming a planar Ni2N2 arrangement. The complex [3](ClO4)(2) is diamagnetic while the complex 2 is paramagnetic. The results of magnetic measurements on the dinickel complex in the temperature range 1.8-300 K are reported. The system can be described as a single spin S = 2 in the low-temperature range T much less than J/k whereas at high temperatures, T much greater than J/k, it behaves as two independent spins S = 1.The reaction of [L-2](-) with K-2[PtCl4], however, yielded a monometailic platinum complex, [PtCl3(L-2)], 5, where the pyridyl nitrogen of the aminopyridyl function remained unused. The X-ray structure of the complex 4a is reported. The bond lengths along the ligand backbones in all the complexes indicate extensive pi-delocalization. Spectral data of the complexes are reported and compared. [References: 28]
机译：通过钴介导的配位NH4C5N = NC6H5的苯环胺化反应，合成了一种新的多齿桥联配体NH4C5N = NC6H4N（H）C5H4N（HL2）。分离并表征了绿色钴络合物中间体[Co（L-2）（2）]（ClO4），[1]（ClO4）和游离配体HL2。报告了[H2L2]（ClO4）的X射线结构。脱质子后，该配体表现为桥接配体。它与NiCl2-6H（2）O和Na-2 [PdCl4]反应生成双金属配合物[Ni2Cl2（L-2）（2）]，2和[Pd-2（L-2）（2）]。 （ClO4）（2），[3]（ClO4）（2）。报道了这两种双金属配合物的X射线结构。双镍配合物的结构尤其独特。在该络合物中，两个[L2]（-）配体的两个去质子化仲胺氮与两个镍中心键合，同时形成平面Ni2N2排列。配合物[3]（ClO4）（2）是抗磁性的，而配合物2是顺磁性的。报告了在1.8-300 K的温度范围内对二镍配合物进行磁性测量的结果。该系统可以描述为在低温范围T远小于J / k的单个自旋S = 2，而在高温情况下T远大于J / k的T表现为两个独立的自旋S = 1。 [L-2]（-）与K-2 [PtCl4]的混合物，生成了单金属铂配合物[PtCl3（L-2）]，5，其中氨基吡啶基官能团的吡啶基氮尚未使用。报告了配合物4a的X射线结构。在所有配合物中沿着配体主链的键长表明大量的π-离域。报告并比较了配合物的光谱数据。 [参考：28]

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