Herein, we report the synthesis of two novel ionic Ti complexes possessing three [N,O]-type bidentate ligands from the reaction of Fe metallascorpionate ligands possessing extended alcohol groups and TiCl₄. The reaction of substituted hydroxyphenyl tetrazole and Fe(ClO₄)₃ in a molar ratio of 3:1 afforded iron scorpionate metalloligands possessing extended arms, which were characterized by IR spectroscopy and ESI-TOF-MS spectrometry. Their molecular structures were also confirmed as neutral Fe-centered scorpionate complexes by X-ray crystallography, in which the extended alcohol groups adopted a tripodal geometry. Moreover, two different crystals of iron scorpionate metalloligand grown from CH₂Cl₂ and CH₃OH were studied, revealing that, in the latter crystal, the tripod arms are folded and aligned toward the C₃-rotational axis of the molecule, whereas the tripod arms are unfolded and spread outward from the rotational axis in the former crystal. These metalloligands are solvatochromatic; a bathochromic shift was observed as the solvent polarity increased. From the reaction, the aforesaid Fe complexes were further reacted with TiCl₄ in a molar ratio of 1:1 to produce ionic [TiL₃]⁺[FeCl₄]⁻ (L = substituted hydroxyphenyl tetrazole) complexes from the transmetalation of Ti and Fe. The complexes were characterized by various analytical methods including UV/vis and IR spectroscopies, electrospray time-of-flight mass spectrometry (ESI-TOF-MS), and X-ray crystallography.

中文翻译：

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具有三个[N，O]型四唑基配体的阳离子Ti配合物：Fe Metallascorpionate配合物中的Ti↔Fe过渡金属化

在本文中，我们报道了具有3个[N，O]型双齿配体的新型离子型Ti配合物的合成，这些配合物是由具有延伸的醇基的Fe2金属蝎子配体与TiCl _{4反应制得的}。取代的羟基苯基四唑与Fe（ClO ₄）₃摩尔比为3：1的反应，得到了具有延伸臂的蝎铁金属配体，通过红外光谱和ESI-TOF-MS光谱对其进行了表征。X射线晶体学也证实了它们的分子结构为中性的以铁为中心的蝎形配合物，其中扩展的醇基采用了三脚架的几何形状。此外，从CH ₂ Cl ₂和CH中生长出两种不同的蝎铁酸金属配体晶体研究了₃ OH，发现在后一种晶体中，三脚架臂折叠并朝向分子的C _3-旋转轴排列，而在前一种晶体中，三脚架臂展开并从旋转轴向外扩展。这些金属配体是溶剂合色的。随着溶剂极性的增加，出现了红移。通过该反应，使上述Fe络合物以1：1的摩尔比与TiCl ₄进一步反应，生成离子性的[Ti L ₃ ] ⁺ [FeCl ₄ ] ^-（LTi和Fe的重金属化生成=取代的羟基苯基四唑）配合物。通过多种分析方法对复合物进行表征，包括紫外/可见光谱和红外光谱，电喷雾飞行时间质谱（ESI-TOF-MS）和X射线晶体学。