Thiolate-Thione Redox-Active Ligand with a Six-Membered Chelate Ring via Template Condensation and Its Pt(II) Complexes
Thiolate-Thione Redox-Active Ligand with a Six-Membered Chelate Ring via Template Condensation and Its Pt(II) Complexes
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DOI：
10.1021/acs.inorgchem.1c01693
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发表时间：
2021-08-12
影响因子：
4.6
通讯作者：
Doerrer，Linda H.
中科院分区：
文献类型：
--
作者：
Zuckerman，Linda A.;Vargo，Natasha P.;Doerrer，Linda H.
在Pt（II）、硫代苯甲酰胺和碱的混合物中发现了一种新的模板缩合反应。在类似条件下合成了四种配合物[Pt（ctaPhR）2]，R = CH_3（1a），H（1b），F（1c），Cl（1d），cta =缩合硫代酰胺，并通过~1HNMR，UV-vis-NIR光谱，电化学，元素分析和单晶X-射线衍射进行了表征。配体是氧化还原活性的，并且可以从初始的单阴离子还原为双阴离子，然后是三阴离子状态。1a与[Cp2Co]的化学还原产生[Cp2Co] 2 [Pt（ctaPhCH 3）2]，[Cp2Co] 2 [1a]，其已经通过添加EPR谱和SQUID磁化进行了类似的表征。原位生成了含[1a] 1-的单还原形式（nBu4N）[Pt（ctaPhCH 3）2]，并用紫外-可见光谱和EPR光谱进行了表征。DFT研究1b，[1b] 1-和[1b] 2-证实了额外的电子的位置在专门的配体为基础的轨道。这种氧化还原活性配体的详细分析，强调有利于noninnocent行为的特点，在六元螯合环，包括在内。
A new template condensation reaction has been discovered in a mixture of Pt(II), thiobenzamide, and base. Four complexes of the general form [Pt(ctaPhR)2], R = CH3(1a), H (1b), F(1c), Cl (1d), cta =condensedthioamide, have been prepared under similar conditions and thoroughly characterized by1H NMR and UV–vis-NIR spectroscopy, (spectro)electrochemistry, elemental analysis, and single-crystal X-ray diffraction. The ligand is redox active and can be reduced from the initial monoanion to a dianionic and then trianionic state. Chemical reduction of1awith [Cp2Co] yielded [Cp2Co]2[Pt(ctaPhCH3)2],[Cp2Co]2[1a], which has been similarly characterized with the addition of EPR spectroscopy and SQUID magnetization. The singly reduced form containing[1a]1–, (nBu4N)[Pt(ctaPhCH3)2], has been generated in situ and characterized by UV–vis and EPR spectroscopies. DFT studies of1b,[1b]1–, and[1b]2–confirm the location of additional electrons in exclusively ligand-based orbitals. A detailed analysis of this redox-active ligand, with emphasis on the characteristics that favor noninnocent behavior in six-membered chelate rings, is included.