获得同感性中性和阴离子五坐标Pr(IV)硅氧化物配合物

IF 7.4 1区 化学 Q1 CHEMISTRY, MULTIDISCIPLINARY
Pragati Pandey, Megan Keener, Thayalan Rajeshkumar, Rosario Scopelliti, Andrzej Sienkiewicz, Ivica Zivkovic, Laurent Maron, Marinella Mazzanti
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引用次数: 0

摘要

结构表征的Pr(IV)配合物仅限于四个例子,因为能够稳定Pr(IV)的配体和反应条件仍然难以捉摸。在这里,我们确定了允许合成Pr(IV)配合物的反应条件,最初认为难以分离。三(叔丁基)硅氧化物(-OSi (OtBu)3)和三苯基硅氧化物(-OSiPh3)配体的Pr(IV)配合物,[PrIV(OSi(OtBu)3)4] (2-PrOtBu), [MPrIV(OSiPh3)5] (5M-PrPh) (M = K, Cs),和[KDB18C6][PrIV(OSiPh3)5], (5][KDB18C6- prph])在四和五(硅)镨(III)酸盐配合物,[KPrIII(OSi(OtBu)3)4] (1-PrOtBu)和[M2PrIII(OSiPh3)5] (M = K, Cs)上被分离和充分表征,使用噻吩自由基阳离子四氟硼酸盐氧化剂。thiaBF4。试剂和反应条件的关键作用,如thiaBF4对神奇蓝氧化剂和非配位溶剂对配位溶剂,证明了高价Pr(IV)配合物的分离。研究了该材料的固态结构和电化学性能,并进行了理论计算。通过电子顺磁共振(EPR)和SQUID磁强计进一步证实了Pr(IV)的氧化态。配合物5M-PrPh和5[KDB18C6]-PrPh提供了阴离子Ln(IV)配合物的第一个例子,证明了利用带电Pr(IV)配合物作为操纵氧化还原电位的工具的可能性,从而利用相同的配体获得更稳定的配合物。
本文章由计算机程序翻译,如有差异,请以英文原文为准。
Accessing Homoleptic Neutral and Anionic Five-coordinate Pr(IV) Siloxide Complexes
Structurally characterized Pr(IV) complexes are limited to four examples because the ligands and reaction conditions capable of stabilizing Pr(IV) remain elusive. Here we identify reaction conditions allowing the synthesis of Pr(IV) compelxes that were originally thought difficult to isolate. The Pr(IV) complexes of the tris(tert-butoxy)siloxide (–OSi(OtBu)3) and triphenylsiloxide (–OSiPh3) ligands, [PrIV(OSi(OtBu)3)4] (2-PrOtBu), [MPrIV(OSiPh3)5] (5M-PrPh) (M = K, Cs), and [KDB18C6][PrIV(OSiPh3)5], (5[KDB18C6-PrPh]) were isolated and fully characterized upon the oxidation of the tetrakis and pentakis(siloxide)praseodymium(III) ate complexes, [KPrIII(OSi(OtBu)3)4] (1-PrOtBu) and [M2PrIII(OSiPh3)5] (4M-PrPh) (M = K, Cs), using the thianthrene radical cation tetrafluoroborate oxidant, thiaBF4. The crucial role of reagents and reaction conditions, like thiaBF4 over the magic blue oxidant and non-coordinating over coordinating solvents, are demonstrated for the isolation of high valent Pr(IV) complexes. The solid state structural and electrochemical properties were studied and further augmented with theoretical calculations. The Pr(IV) oxidation state was further confirmed by electron paramagnetic resonance (EPR) and SQUID magnetometry measurements. Complexes 5M-PrPh and 5[KDB18C6]-PrPh provide the first example of anionic Ln(IV) complexes demonstrating the possibility of accessing charged Pr(IV) complexes as a tool to manipulate the redox potential and therefore access to more stable complexes with the same ligand.
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来源期刊
Chemical Science
Chemical Science CHEMISTRY, MULTIDISCIPLINARY-
CiteScore
14.40
自引率
4.80%
发文量
1352
审稿时长
2.1 months
期刊介绍: Chemical Science is a journal that encompasses various disciplines within the chemical sciences. Its scope includes publishing ground-breaking research with significant implications for its respective field, as well as appealing to a wider audience in related areas. To be considered for publication, articles must showcase innovative and original advances in their field of study and be presented in a manner that is understandable to scientists from diverse backgrounds. However, the journal generally does not publish highly specialized research.
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