Covalency in Ce~(IV) and U~(IV) halide and N-heterocyclic carbene bonds

Arnold P.L.; Turner Z.R.; Kaltsoyannis N.; Pelekanaki P.; Bellabarba R.M.; Tooze R.P.

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Covalency in Ce~(IV) and U~(IV) halide and N-heterocyclic carbene bonds

机译：Ce〜（IV）和U〜（IV）卤化物和N-杂环卡宾键的共价

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Oxidative halogenation with trityl chloride provides convenient access to Ce~(IV) and U~(IV) chloroamides [M(N{SiMe_3} _2)_3Cl] and their N-heterocyclic carbene derivatives, [M(L)(N{ SiMe+3}_2)_2Cl] (L=OCMe _2CH_2(CNCH_2- CH_2NDipp) Dipp=2,6-iPr_2C_6H_3). Computational analysis of the bonding in these and a fluoro analogue, [U(L)(N{SiMe_3} _2)_2F], provides new information on the covalency in this relative rare oxidation state for molecular cerium complexes. Computational studies reveal increased Mayer bond orders in the actinide carbene bond compared with the lanthanide carbene bond, and natural and atoms-in-molecules analyses suggest greater overall ionicity in the cerium complexes than in the uranium analogues.

机译：三苯甲基氯的氧化卤化作用提供了便捷的Ce_（IV）和U〜（IV）氯酰胺[M（N {SiMe_3} _2）_3Cl]及其N-杂环卡宾衍生物[M（L）（N {SiMe + 3} _2）_2Cl]（L = OCMe _2CH_2（CNCH_2- CH_2NDipp）Dipp = 2,6-iPr_2C_6H_3）。这些与氟类似物[U（L）（N {SiMe_3} _2）_2F]的键合的计算分析为分子铈配合物在这种相对罕见的氧化态下的共价提供了新的信息。计算研究表明，与镧系元素卡宾键相比，act系元素卡宾键的Mayer键顺序增加，自然和分子内分析表明，铈配合物中的整体离子化程度高于铀类似物。

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《Chemistry: A European journal》 |2010年第31期|共7页
作者
Arnold P.L.; Turner Z.R.; Kaltsoyannis N.; Pelekanaki P.; Bellabarba R.M.; Tooze R.P.;
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正文语种 eng
中图分类应用化学;
关键词
Actinides; Computational chemistry; Covalency; Lanthanides; N-heterocyclic carbenes;

机译：in系元素;计算化学;共价键;镧系元素;N-杂环卡宾;

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1. Covalency in Ce~(IV) and U~(IV) halide and N-heterocyclic carbene bonds [J] . Arnold P.L., Turner Z.R., Kaltsoyannis N., Chemistry: A European journal . 2010,第31期

机译：Ce〜（IV）和U〜（IV）卤化物和N-杂环卡宾键的共价
2. Emergence of comparable covalency in isostructural cerium(IV)- and uranium(IV)-carbon multiple bonds [J] . Gregson Matthew, Lu Erli, Tuna Floriana, Chemical science . 2016,第5期

机译：异结构铈（IV）-和铀（IV）-碳多重键中可比价的出现
3. Emergence of comparable covalency in isostructural cerium(IV)– and uranium(IV)–carbon multiple bonds [J] . Matthew Gregson, Erli Lu, Floriana Tuna, Chemical science . 2016,第5期

机译：同学铈（IV）和铀（IV）中可比核的出现 - 碳多键
4. N-Heterocyclic Carbene Adducts of High-Oxidation-State Metal Halides: An Unexpected Instance of Lewis Acidic Ccarbene Character [C] . Mark D. Spicer, Christopher A. Dodds, John P. Culver, American Chemical Society . 2006

机译：高氧化态金属卤化物的N-杂环配子：Lewis酸性Ccarbene特征的意外情况
5. Catalytic C-H Bond Functionalization by Nickel(0) N-Heterocyclic Carbene Complexes: Influence of Ligand Sterics on Selective Silylation [D] . Elsby, Matthew Ryan. 2017

机译：镍（0）N-杂环碳烯络合物的催化C-H键官能化：配体的立体异构体对选择性硅烷化的影响
6. Emergence of comparable covalency in isostructural cerium(iv)– and uranium(iv)–carbon multiple bonds [O] . Matthew Gregson, Erli Lu, Floriana Tuna, 2018

机译：等结构铈（iv）–和铀（iv）–碳多重键中可比价的出现
7. Covalency in Ce-IV and U-IV Halide and N-Heterocyclic Carbene Bonds [O] . Arnold, Polly L, Turner, Zoe R, Kaltsoyannis, Nikolas, 2010

机译：Ce-IV和U-IV卤化物和N-杂环卡宾键的共价
8. Bonding Studies of Compounds of Boron and the Group III and IV Elements. XII. Variable Temperature He I Photoelectron Spectra of Group III Halides, 2MX3 -- M2X6 (M = Al or Ga, X = Cl, Br, or I). [R] . Lappert, M. F., Pedley, J. B., Sharp, G. J., 1974

机译：硼化合物与III族和IV族元素的键合研究。十二。可变温度He I III族卤化物，2mX3-m2X6（m = al或Ga，X = Cl，Br或I）的光电子能谱。

Covalency in Ce~(IV) and U~(IV) halide and N-heterocyclic carbene bonds

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