Exploring Spin-Orbit Effects in a [Cu6Tl]+ Nanocluster Featuring an Uncommon Tl-H Interaction

被引：1

作者：

Hertler, Phoebe R. ^{[1
]}

Yu, Xiaojuan ^{[2
]}

Brower, Jordan D. ^{[1
]}

Nguyen, Thuy-Ai D. ^{[1
]}

Wu, Guang ^{[1
]}

Autschbach, Jochen ^{[2
]}

Hayton, Trevor W. ^{[1
]}

机构：

[1] Univ Calif Santa Barbara, Dept Chem & Biochem, Santa Barbara, CA 93106 USA

[2] Univ Buffalo State Univ New York, Dept Chem, Buffalo, NY 14260 USA

来源：

CHEMISTRY-A EUROPEAN JOURNAL | 2024年 / 30卷 / 25期

基金：

美国国家科学基金会;

关键词：

cluster compounds; copper; density functional theory; hydrides; thallium; INFRARED-SPECTRA; NMR-SPECTROSCOPY; CHEMICAL-SHIFTS; PROBE COVALENCY; HYDRIDES; COMPLEXES; THALLIUM; CLUSTERS; PB; APPROXIMATION;

D O I：

10.1002/chem.202400390

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

Reaction of [CuH(PPh3)](6) with 1 equiv. of Tl(OTf) results in formation of [Cu6TlH6(PPh3)(6)][OTf] (<bold>[1]OTf]</bold>), which can be isolated in good yields. Variable-temperature H-1 NMR spectroscopy, in combination with density functional theory (DFT) calculations, confirms the presence of a rare Tl-H orbital interaction. According to DFT, the H-1 chemical shift of the Tl-adjacent hydride ligands of <bold>[1]</bold>(+) includes 7.7 ppm of deshielding due to spin-orbit effects from the heavy Tl atom. This study provides valuable new insights into a rare class of metal hydrides, given that <bold>[1][OTf]</bold> is only the third isolable species reported to contain a Tl-H interaction.

引用

页数：5

共 72 条

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