Compression of curium pyrrolidine-dithiocarbamate enhances covalency

Sperling Joseph M.; Warzecha Evan J.; Celis-Barros Cristian; Sergentu Dumitru-Claudiu; Wang Xiaoyu; Klamm Bonnie E.; Windorff Cory J.; Gaiser Alyssa N.; White Frankie D.; Beery Drake A.; Chemey Alexander T.; Whitefoot Megan A.; Long Brian N.; Hanson Kenneth; Koegerler Paul; Speldrich Manfred; Zurek Eva; Autschbach Jochen; Albrecht-Schonzart Thomas E.

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Compression of curium pyrrolidine-dithiocarbamate enhances covalency

机译：吡咯烷 - 二硫代氨基甲酸甲酯的压缩增强了共价

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Enhanced covalency is achieved for a curium complex with curium-sulfur bonds by subjecting the compound to high pressures, indicating that pressure can be used to tune covalency in actinide compounds.Curium is unique in the actinide series because its half-filled 5f (7)shell has lower energy than other 5f (n)configurations, rendering it both redox-inactive and resistant to forming chemical bonds that engage the 5fshell(1-3). This is even more pronounced in gadolinium, curium's lanthanide analogue, owing to the contraction of the 4forbitals with respect to the 5forbitals(4). However, at high pressures metallic curium undergoes a transition from localized to itinerant 5felectrons(5). This transition is accompanied by a crystal structure dictated by the magnetic interactions between curium atoms(5,6). Therefore, the question arises of whether the frontier metal orbitals in curium(iii)-ligand interactions can also be modified by applying pressure, and thus be induced to form metal-ligand bonds with a degree of covalency. Here we report experimental and computational evidence for changes in the relative roles of the 5f/6dorbitals in curium-sulfur bonds in [Cm(pydtc)(4)](-)(pydtc, pyrrolidinedithiocarbamate) at high pressures (up to 11 gigapascals). We compare these results to the spectra of [Nd(pydtc)(4)](-)and of a Cm(iii) mellitate that possesses only curium-oxygen bonds. Compared with the changes observed in the [Cm(pydtc)(4)](-)spectra, we observe smaller changes in thef-ftransitions in the [Nd(pydtc)(4)](-)absorption spectrum and in thef-femission spectrum of the Cm(iii) mellitate upon pressurization, which are related to the smaller perturbation of the nature of their bonds. These results reveal that the metal orbital contributions to the curium-sulfur bonds are considerably enhanced at high pressures and that the 5forbital involvement doubles between 0 and 11 gigapascal. Our work implies that covalency in actinides is complex even when dealing with the same ion, but it could guide the selection of ligands to study the effect of pressure on actinide compounds.

机译：通过使化合物对高压进行含有柠檬键的含有含有含含含氟键的含有增强的共价，表明压力可用于曲调化合物中的共价。蓖麻序列是独特的，因为它的半填充5f（7）壳体的能量低于其他5F（n）配置，使其氧化还原氧化氧掺杂和耐抗体形成5fshell（1-3）的化学键。由于4个关于5米碧珠（4）的4个碧玺的收缩，这在钆镧系元素类似物中更加明显。然而，在高压下，金属含有经历从局部化到Itinerant 5f电磁子（5）的过渡。该转变伴随着通过甲状原子（5,6）之间的磁相互作用而指定的晶体结构。因此，通过施加压力来改变含含量（III）--ligand相互作用的前沿金属轨道的问题，从而诱导与含有共价的金属 - 配体键形成金属 - 配体键。在这里，我们报告了在高压下[cm（pydtc）（4）（4）（4）（pydtc，吡咯烷二氨基甲酸）的柠檬键中的5f / 6ddorbinals的相对作用的变化的实验和计算证据（pydtc，吡咯烷硫代氨基甲酸盐）（最多11种gigapascals）。将这些结果与仅具有含锡氧键的[ND（PYDTC）（4）（4）（4）（4）（4））和蜂鸣的梅尔的光谱进行比较。与[cm（pydtc）（4）]（ - ）光谱中观察到的变化相比，我们观察[ND（PyDTC）]（ - ）吸收光谱和THEF-Pshience中的F-Ftransitions的较小变化CM（III）的光谱在加压时均匀，与其键的性质的较小扰动有关。这些结果表明，在高压下，对含硫键的金属轨道贡献显着增强，并且5型血管曲线介于0至11个千兆卡帕尔之间。我们的作品意味着即使在处理相同的离子时，散落物中的共价也很复杂，但它可以指导选择配体以研究压力对致动曲线化合物的影响。

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《Nature》 |2020年第7816期|396-399|共4页
作者
Sperling Joseph M.; Warzecha Evan J.; Celis-Barros Cristian; Sergentu Dumitru-Claudiu; Wang Xiaoyu; Klamm Bonnie E.; Windorff Cory J.; Gaiser Alyssa N.; White Frankie D.; Beery Drake A.; Chemey Alexander T.; Whitefoot Megan A.; Long Brian N.; Hanson Kenneth; Koegerler Paul; Speldrich Manfred; Zurek Eva; Autschbach Jochen; Albrecht-Schonzart Thomas E.;
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作者单位

Florida State Univ Dept Chem Biochem Tallahassee FL USA;

Florida State Univ Dept Chem Biochem Tallahassee FL USA;

Florida State Univ Dept Chem Biochem Tallahassee FL USA;

Univ Buffalo State Univ New York Dept Chem Buffalo NY USA;

Univ Buffalo State Univ New York Dept Chem Buffalo NY USA;

Florida State Univ Dept Chem Biochem Tallahassee FL USA;

Florida State Univ Dept Chem Biochem Tallahassee FL USA;

Florida State Univ Dept Chem Biochem Tallahassee FL USA;

Florida State Univ Dept Chem Biochem Tallahassee FL USA;

Florida State Univ Dept Chem Biochem Tallahassee FL USA;

Florida State Univ Dept Chem Biochem Tallahassee FL USA;

Florida State Univ Dept Chem Biochem Tallahassee FL USA;

Florida State Univ Dept Chem Biochem Tallahassee FL USA;

Florida State Univ Dept Chem Biochem Tallahassee FL USA;

Rhein Westfal TH Aachen Institut Anorganische Chem Aachen Germany;

Florida State Univ Dept Chem Biochem Tallahassee FL USA|Rhein Westfal TH Aachen Institut Anorganische Chem Aachen Germany;

Florida State Univ Dept Chem Biochem Tallahassee FL USA|Univ Buffalo State Univ New York Dept Chem Buffalo NY USA;

Florida State Univ Dept Chem Biochem Tallahassee FL USA|Univ Buffalo State Univ New York Dept Chem Buffalo NY USA;

Florida State Univ Dept Chem Biochem Tallahassee FL USA;

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收录信息美国《科学引文索引》(SCI);美国《工程索引》(EI);美国《生物学医学文摘》(MEDLINE);美国《化学文摘》(CA);
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Compression of curium pyrrolidine-dithiocarbamate enhances covalency

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