The reductive coupling of dinitrogen

被引:215
作者
Legare, Marc-Andre [1 ,2 ]
Rang, Maximilian [1 ,2 ]
Belanger-Chabot, Guillaume [1 ,2 ]
Schweizer, Julia I. [3 ]
Krummenacher, Ivo [1 ,2 ]
Bertermann, Rudiger [1 ,2 ]
Arrowsmith, Merle [1 ,2 ]
Holthausen, Max C. [3 ]
Braunschweig, Holger [1 ,2 ]
机构
[1] Julius Maximilians Univ Wurzburg, Inst Inorgan Chem, D-97074 Wurzburg, Germany
[2] Julius Maximilians Univ Wurzburg, Inst Sustainable Chem & Catalysis Boron, D-97074 Wurzburg, Germany
[3] Goethe Univ, Inst Inorgan & Analyt Chem, Max von Laue Str 7, D-60438 Frankfurt, Germany
基金
加拿大自然科学与工程研究理事会;
关键词
STATE PERTURBATION-THEORY; GAUSSIAN-BASIS SETS; DIRADICAL CHARACTER; CRYSTAL-STRUCTURE; HIGH-PRESSURE; HARTREE-FOCK; NITROGEN; CHEMISTRY; DENSITY; ENERGY;
D O I
10.1126/science.aav9593
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 coupling of two or more molecules of dinitrogen (N-2) occurs naturally under the radiative conditions present in the ionosphere and may be achieved synthetically under ultrahigh pressure or plasma conditions. However, the comparatively low N-N single-bond enthalpy generally renders the catenation of the strongly triple-bonded N-2 diatomic unfavorable and the decomposition of nitrogen chains a common reaction motif. Here, we report the surprising organoboron-mediated catenation of two N-2 molecules under near-ambient conditions to form a complex in which a [N-4](2-) chain bridges two boron centers. The reaction entails reductive coupling of two hypovalent-boron-bound N-2 units in a single step. Both this complex and a derivative protonated at both ends of the chain were characterized crystallographically.
引用
收藏
页码:1329 / +
页数:78
相关论文
共 72 条
[1]  
Albrecht T, 1998, Z ANORG ALLG CHEM, V624, P1514, DOI 10.1002/(SICI)1521-3749(199809)624:9<1514::AID-ZAAC1514>3.0.CO
[2]  
2-5
[3]  
Andrienko G. A., 2015, CHEMCRAFT
[4]   Introduction of n-electron valence states for multireference perturbation theory [J].
Angeli, C ;
Cimiraglia, R ;
Evangelisti, S ;
Leininger, T ;
Malrieu, JP .
JOURNAL OF CHEMICAL PHYSICS, 2001, 114 (23) :10252-10264
[5]   n-electron valence state perturbation theory:: A spinless formulation and an efficient implementation of the strongly contracted and of the partially contracted variants [J].
Angeli, C ;
Cimiraglia, R ;
Malrieu, JP .
JOURNAL OF CHEMICAL PHYSICS, 2002, 117 (20) :9138-9153
[6]   N-electron valence state perturbation theory:: a fast implementation of the strongly contracted variant [J].
Angeli, C ;
Cimiraglia, R ;
Malrieu, JP .
CHEMICAL PHYSICS LETTERS, 2001, 350 (3-4) :297-305
[7]   SYNTHESES AND SPECTROSCOPIC CHARACTERISTICS OF BIS-[DIMETHYL(ARYL)SILYLMETHYL]PLATINUM(II) AND BIS-[DIMETHYL(BENZYL)-SILYLMETHYL]PLATINUM(II) COMPLEXES WITH DIENE-DONOR, NITROGEN-DONOR, AND PHOSPHORUS-DONOR LIGANDS [J].
ANKIANIEC, BC ;
YOUNG, GB .
POLYHEDRON, 1995, 14 (02) :249-265
[8]  
Armarego WLF, 2009, PURIFICATION OF LABORATORY CHEMICALS, 6TH EDITION, P1
[9]   Theoretical evidence for the singlet diradical character of square planar nickel complexes containing two ο-semiquinonato type ligands [J].
Bachler, V ;
Olbrich, G ;
Neese, F ;
Wieghardt, K .
INORGANIC CHEMISTRY, 2002, 41 (16) :4179-4193
[10]   The Fractional Occupation Number Weighted Density as a Versatile Analysis Tool for Molecules with a Complicated Electronic Structure [J].
Bauer, Christoph Alexander ;
Hansen, Andreas ;
Grimme, Stefan .
CHEMISTRY-A EUROPEAN JOURNAL, 2017, 23 (25) :6150-6164