Park Yu Jin, Ryu Ji Yeon, Hwang Sam, Park Ka Hyun, Lee Ji Min, Cho Sung, Lee Sunwoo, Saha Manik Lal, Stang Peter J, Lee Junseong
Department of Chemistry, Chonnam National University , Gwangju 61186, Republic of Korea.
Department of Chemistry, University of Utah , 315 South 1400 East, Room 2020, Salt Lake City, Utah 84112, United States.
Inorg Chem. 2017 Nov 20;56(22):14060-14068. doi: 10.1021/acs.inorgchem.7b02209. Epub 2017 Nov 9.
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 TiCl. The reaction of substituted hydroxyphenyl tetrazole and Fe(ClO) 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 CHCl and CHOH were studied, revealing that, in the latter crystal, the tripod arms are folded and aligned toward the C-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 TiCl in a molar ratio of 1:1 to produce ionic [TiL][FeCl] (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.
在此，我们报道了由具有延长醇基的铁金属蝎形配体与TiCl反应合成了两种新型离子型钛配合物，其具有三个[N,O]型双齿配体。取代的羟基苯基四唑与Fe(ClO)以3:1的摩尔比反应，得到了具有延长臂的铁蝎形金属配体，通过红外光谱和电喷雾飞行时间质谱（ESI-TOF-MS）对其进行了表征。通过X射线晶体学也证实了它们的分子结构为以中性铁为中心的蝎形配合物，其中延长的醇基呈三脚架几何形状。此外，研究了从CHCl和CHOH中生长出的两种不同的铁蝎形金属配体晶体，结果表明，在后者的晶体中，三脚架臂折叠并朝向分子的C旋转轴排列，而在前者的晶体中，三脚架臂展开并从旋转轴向外伸展。这些金属配体具有溶剂化显色性；随着溶剂极性的增加，观察到红移。通过该反应，上述铁配合物进一步与TiCl以1:1的摩尔比反应，通过Ti和Fe的金属转移反应生成离子型[TiL][FeCl]（L = 取代的羟基苯基四唑）配合物。通过包括紫外/可见光谱和红外光谱、电喷雾飞行时间质谱（ESI-TOF-MS）以及X射线晶体学在内的各种分析方法对这些配合物进行了表征。
