Dinitrogen complexation and reduction at low-valent calcium

被引：164

作者：

Roesch, B. ^{[1
]}

Gentner, T. X. ^{[1
]}

Langer, J. ^{[1
]}

Faerber, C. ^{[1
]}

Eyselein, J. ^{[1
]}

Zhao, L. ^{[2
]}

Ding, C. ^{[2
]}

Frenking, G. ^{[2
,3
]}

Harder, S. ^{[1
]}

机构：

[1] Univ Erlangen Nurnberg, Inorgan Chem, D-91058 Erlangen, Germany

[2] Nanjing Tech Univ, Sch Chem & Mol Engn, Inst Adv Synth, Nanjing 211816, Peoples R China

[3] Philipps Univ Marburg, Fachbereich Chem, D-35043 Marburg, Germany

来源：

SCIENCE | 2021年 / 371卷 / 6534期

基金：

中国国家自然科学基金;

关键词：

MAGNESIUM(I) COMPOUNDS; BASIS-SETS; ENERGY; BOND; APPROXIMATION; ACTIVATION; NITROGEN; SR;

D O I：

10.1126/science.abf2374

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：

Here we report that attempted preparation of low-valent Ca-I complexes in the form of LCa-CaL (where L is a bulky beta-diketiminate ligand) under dinitrogen (N-2) atmosphere led to isolation of LCa(N-2)CaL, which was characterized crystallographically. The N-2(2-) anion in this complex reacted in most cases as a very potent two-electron donor. Therefore, LCa(N-2)CaL acts as a synthon for the low-valent Ca-I complex LCa-CaL, which was the target of our studies. The N-2(2-) anion could also be protonated to diazene ( N2H2) that disproportionated to hydrazine and N-2. The role of Ca d orbitals for N-2 activation is discussed.

引用

页码：1125 / +

页数：157

共 50 条

[11] A Crystalline Mesoionic Diazasilole Featuring Low-Valent Silicon
Lan, Xiaofang
Wang, Hongyu
Liang, Qiuming
Liu, Liu Leo
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2025, 64 (03)
[12] The oxidation state in low-valent beryllium and magnesium compounds
Gimferrer, Marti
Danes, Sergi
Vos, Eva
Yildiz, Cem B.
Corral, Ines
Jana, Anukul
Salvador, Pedro
Andrada, Diego M.
CHEMICAL SCIENCE, 2022, 13 (22) : 6583 - 6591
[13] Hydrogenolysis of Polysilanes Catalyzed by Low-Valent Nickel Complexes
Pribanic, Bruno
Trincado, Monica
Eiler, Frederik
Vogt, Matthias
Comas-Vives, Aleix
Grutzmacher, Hansjorg
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2020, 59 (36) : 15603 - 15609
[14] Formation of cyanates in low-valent uranium chemistry: a synergistic experimental/theoretical study
Kefalidis, Christos E.
Frey, Alistair S. P.
Roe, S. Mark
Cloke, F. Geoffrey N.
Maron, Laurent
DALTON TRANSACTIONS, 2014, 43 (29) : 11202 - 11208
[15] Self-Alignment of Low-Valent Octanuclear Palladium Atoms
Nakamae, Kanako
Takemura, Yukie
Kure, Bunsho
Nakajima, Takayuki
Kitagawa, Yasutaka
Tanase, Tomoaki
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2015, 54 (03) : 1016 - 1021
[16] Applications of Low-Valent Transition Metalates: Development of a Reactive Noncarbonyl Rhenium(I) Anion
Ouellette, Erik T.
Magdalenski, Julian S.
Bergman, Robert G.
Arnold, John
ACCOUNTS OF CHEMICAL RESEARCH, 2022, 55 (05) : 783 - 793
[17] Dinitrogen complexation with main group radicals
Kurzbach, Dennis
Sharma, Ajay
Sebastiani, Daniel
Klinkhammer, Karl W.
Hinderberger, Dariush
CHEMICAL SCIENCE, 2011, 2 (03) : 473 - 479
[18] Low-valent zirconocene-mediated cyclization of γ,δ-unsaturated oximes
Kitamura, Mitsuru
Shintaku, Yuki
Kudo, Daisuke
Okauchi, Tatsuo
TETRAHEDRON LETTERS, 2010, 51 (37) : 4890 - 4893
[19] Theoretical design and exploration of low-valent uranium metallocenes via manipulating cyclopentadienyl substituent
Su, Dong-Mei
Cai, Hong-Xue
Zheng, Xiu-Jun
Niu, Shuai
Pan, Qing-Jiang
COMPUTATIONAL AND THEORETICAL CHEMISTRY, 2021, 1195
[20] Reductive Coupling of Xylyl Isocyanide Mediated by Low-Valent Uranium
Staun, Selena L.
Kent, Greggory T.
Gomez-Torres, Alejandra
Wu, Guang
Fortier, Skye
Hayton, Trevor W.
ORGANOMETALLICS, 2021, 40 (17) : 2934 - 2938

← 1 2 3 4 5 →