Synthesis and Structure of a Terminal Uranium Nitride Complex

被引：271

作者：

King, David M. ^{[1
]}

Tuna, Floriana ^{[2
,3
]}

McInnes, Eric J. L. ^{[2
,3
]}

McMaster, Jonathan ^{[1
]}

Lewis, William ^{[1
]}

Blake, Alexander J. ^{[1
]}

Liddle, Stephen T. ^{[1
]}

机构：

[1] Univ Nottingham, Sch Chem, Nottingham NG7 2RD, England

[2] Univ Manchester, Sch Chem, Manchester M13 9PL, Lancs, England

[3] Univ Manchester, Photon Sci Inst, Manchester M13 9PL, Lancs, England

来源：

SCIENCE | 2012年 / 337卷 / 6095期

基金：

英国工程与自然科学研究理事会; 欧洲研究理事会;

关键词：

INFRARED-SPECTRA; AZIDE; ACTIVATION; MOLECULES; ANALOGS; NUO+;

D O I：

10.1126/science.1223488

中图分类号：

O [数理科学和化学]; P [天文学、地球科学]; Q [生物科学]; N [自然科学总论];

学科分类号：

07 ; 0710 ; 09 ;

摘要：

The terminal uranium nitride linkage is a fundamental target in the study of f-orbital participation in metal-ligand multiple bonding but has previously eluded characterization in an isolable molecule. Here, we report the preparation of the terminal uranium(V) nitride complex [UN(Tren(TIPS))][Na(12-crown-4)(2)] {in which Tren(TIPS) = [N(CH2CH2NSiPr3i)(3)](3-)and Pr-i = CH(CH3)(2)} by reaction of the uranium(III) complex [U(Tren(TIPS))] with sodium azide followed by abstraction and encapsulation of the sodium cation by the polydentate crown ether 12-crown-4. Single-crystal x-ray diffraction reveals a uranium-terminal nitride bond length of 1.825(15) angstroms (where 15 is the standard uncertainty). The structural assignment is supported by means of N-15-isotopic labeling, electronic absorption spectroscopy, magnetometry, electronic structure calculations, elemental analyses, and liberation of ammonia after treatment with water.

引用

页码：717 / 720

页数：4

共 29 条

[1] Simple NUF3 and PUF3 molecules with triple bonds to uranium
Andrews, Lester
Wang, Xuefeng
Lindh, Roland
Roos, Bjoern O.
Marsden, Colin J.
[J]. ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2008, 47 (29) : 5366 - 5370
[2] Carbon dioxide activation with sterically pressured mid- and high-valent uranium complexes
Bart, Suzanne C.
Anthon, Christian
Heinemann, Frank W.
Bill, Eckhard
Edelstein, Norman M.
Meyer, Karsten
[J]. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2008, 130 (37) : 12536 - 12546
[3] Uranium-Carbon Multiple Bonding: Facile Access to the Pentavalent Uranium Carbene [U{C(PPh2NSiMe3)2}(Cl)2(I)] and Comparison of UV=C and UIV=C Bonds
Cooper, Oliver J.
Mills, David P.
McMaster, Jonathan
Moro, Fabrizio
Davies, E. Stephen
Lewis, William
Blake, Alexander J.
Liddle, Stephen T.
[J]. ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2011, 50 (10) : 2383 - 2386
[4] The vitality of uranium molecular chemistry at the dawn of the XXIst century
Ephritikhine, Michel
[J]. DALTON TRANSACTIONS, 2006, (21) : 2501 - 2516
[5] Analysis of uranium azide and nitride complexes by atmospheric pressure chemical ionization mass spectrometry
Evans, William J.
Miller, Kevin A.
Ziller, Joseph W.
Greaves, John
[J]. INORGANIC CHEMISTRY, 2007, 46 (19) : 8008 - 8018
[6] Molecular octa-uranium rings with alternating nitride and azide bridges
Evans, WJ
Kozimor, SA
Ziller, JW
[J]. SCIENCE, 2005, 309 (5742) : 1835 - 1838
[7] Synthesis of a Phosphorano-Stabilized U(IV)-Carbene via One-Electron Oxidation of a U(III)-Ylide Adduct
Fortier, Skye
Walensky, Justin R.
Wu, Guang
Hayton, Trevor W.
[J]. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2011, 133 (18) : 6894 - 6897
[8] Synthesis of a Nitrido-Substituted Analogue of the Uranyl Ion, [N=U=O]+
Fortier, Skye
Wu, Guang
Hayton, Trevor W.
[J]. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2010, 132 (20) : 6888 - +
[9] Towards uranium catalysts
Fox, Alexander R.
Bart, Suzanne C.
Meyer, Karsten
Cummins, Christopher C.
[J]. NATURE, 2008, 455 (7211) : 341 - 349
[10] Uranium Nitrogen Multiple Bonding: Isostructural Anionic, Neutral, and Cationic Uranium Nitride Complexes Featuring a Linear U=N=U Core
Fox, Alexander R.
Arnold, Polly L.
Cummins, Christopher C.
[J]. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2010, 132 (10) : 3250 - +

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