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Structural and Oxidation State Alternatives in Platinum and Palladium Complexes of a Redox‐Active Amidinato Ligand
Chemistry - A European Journal ( IF 3.9 ) Pub Date : 2020-09-21 , DOI: 10.1002/chem.202003636
Fabian Ehret 1 , Vasileios Filippou 1 , Svenja Blickle 1 , Martina Bubrin 1 , Stanislav Záliš 2 , Wolfgang Kaim 1
Affiliation  

Reaction of [Pt(DMSO)2Cl2] or [Pd(MeCN)2Cl2] with the electron‐rich LH=N,N’‐bis(4‐dimethylaminophenyl)ethanimidamide yielded mononuclear [PtL2] (1) but dinuclear [Pd2L4] (2), a paddle‐wheel complex. The neutral compounds were characterized through experiments (crystal structures, electrochemistry, UV‐vis‐NIR spectroscopy, magnetic resonance) and TD‐DFT calculations as metal(II) species with noninnocent ligands L. The reversibly accessible cations [PtL2]+ and [Pd2L4]+ were also studied, the latter as [Pd2L4][B{3,5‐(CF3)2C6H3}4] single crystals. Experimental and computational investigations were directed at the elucidation of the electronic structures, establishing the correct oxidation states within the alternatives [PtII(L)2] or [Pt.(L )2], [PtII(L0.5−)2]+ or [PtIII(L)2]+, [(PdII)2(μ‐L)4] or [(Pd1.5)2(μ‐L0.75−)4], and [(Pd2.5)2(μ‐L)4]+ or [(PdII)2(μ‐L0.75−)4]+. In each case, the first alternative was shown to be most appropriate. Remarkable results include the preference of platinum for mononuclear planar [PtL2] with an N‐Pt‐N bite angle of 62.8(2)° in contrast to [Pd2L4], and the dimetal (Pd24+→Pd25+) instead of ligand (L→L ) oxidation of the dinuclear palladium compound.

中文翻译:

氧化还原活性A基配体的铂和钯配合物中的结构和氧化态选择

[Pt(DMSO)2 Cl 2 ]或[Pd(MeCN)2 Cl 2 ]与富电子的LH = N,N'-双(4-二甲基氨基苯基)乙酰胺酰胺的反应生成单核[PtL 2 ](1),但双核[Pd 2 L 4 ](2),桨轮复合体。中性化合物通过实验表征(晶体结构,电化学,UV-VIS-NIR光谱,核磁共振)和TD-DFT计算作为金属(II)与noninnocent配体L种类- 。可逆访问的阳离子[PtL 2 ] +和[Pd 2 L 4 ]+也进行了研究,后者为[Pd 2 L 4 ] [B {3,5-(CF 32 C 6 H 3 } 4 ]单晶。实验和计算调查在电子结构的阐明被定向,所述替代品[PT内建立正确的氧化态II(L - 2 ]或[铂(L)2 ],[铂II(L 0.5-2 ] +或[PT III(L - 2 ] +,[(Pd II2(μ‐L 4 ]或[(Pd 1.52(μ‐L 0.75−4 ]和[(Pd 2.52(μ‐L 4 ] +或[ (Pd II2μL0.75−4 ] +。在每种情况下,第一种选择都被证明是最合适的。了显着效果包括铂单核平面专利文献的偏好2 ]与Ñ 62.8 -Pt-N咬入角(2)°对比[钯2大号4 ],和双金属(钯2 4+ →PD 2 5+代替配体)(L - →L)双核钯化合物的氧化。
更新日期:2020-09-21
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