Synthesis of a Crystalline Molecular Complex of Y2+, [(18-crown-6)K][(C5H4SiMe3)3Y]

被引：138

作者：

MacDonald, Matthew R. ^{[1
]}

Ziller, Joseph W. ^{[1
]}

Evans, William J. ^{[1
]}

机构：

[1] Univ Calif Irvine, Dept Chem, Irvine, CA 92697 USA

来源：

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY | 2011年 / 133卷 / 40期

基金：

美国国家科学基金会;

关键词：

DINITROGEN REDUCTION; CHEMISTRY; SYSTEM; TM(II); LIGAND; CP''; LA; LN; COORDINATION; LANTHANIDES;

D O I：

10.1021/ja207151y

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

The La2+ complex [K(18-crown-6)(OEt2)]-[Cp '' La-3] (1) [Cp '' = C5H3(SiMe3)(2)-1,3], can be synthesized under N-2, but in the presence of KC5Me5, 1 reduces N-2 to the (N=N)(2-) product [(C5Me5)(2)(THF)La](2)(mu-eta(2):- eta(2)-N-2). This suggests a dichotomy in terms of ligands that optimize isolation of reduced dinitrogen complexes versus isolation of divalent complexes of the rare earths. To determine whether the first crystalline molecular Y2+ complex could be isolated using this logic, Cp'Y-3 (2) (Cp' = C5H4SiMe3) was synthesized from YCl3 and KCp' and reduced with KC8 in the presence of 18-crown-6 in Et2O at -45 degrees C under argon. EPR evidence was consistent with Y2+ and crystallization provided the first structurally characterizable molecular Y2+ complex, dark-maroon-purple [(18-crown-6)K] [Cp'Y-3] (3).

引用

页码：15914 / 15917

页数：4

共 49 条

[1] STUDY OF THE INTERMEDIATE JAHN-TELLER SYSTEM LA-2+ IN CAF2 BY RAMAN AND ELECTRON-PARAMAGNETIC-RES SPECTROSCOPY [J].

BILL, H ;

PILLA, O .

JOURNAL OF PHYSICS C-SOLID STATE PHYSICS, 1984, 17 (18) :3263-3267

[2] Molecular compounds of "new" divalent lanthanides [J].

Bochkarev, MN .

COORDINATION CHEMISTRY REVIEWS, 2004, 248 (9-10) :835-851

[3] The fixation and reduction of dinitrogen using lanthanides: praseodymium and neodymium meso-octaethylporphyrinogen-dinitrogen complexes [J].

Campazzi, E ;

Solari, E ;

Floriani, C ;

Scopelliti, R .

CHEMICAL COMMUNICATIONS, 1998, (23) :2603-2604

[4] Segmented contraction scheme for small-core lanthanide pseudopotential basis sets [J].

Cao, XY ;

Dolg, M .

JOURNAL OF MOLECULAR STRUCTURE-THEOCHEM, 2002, 581 :139-147

[5] Synthesis and characterization of organolanthanidocene(III) (Ln = La, Ce, Pr, Nd) complexes containing the 1,4-cyclohexa-2,5-dienyl ligand (benzene 1,4-dianion):: Structures of [K([18]-crown-6)][Ln{η5-C5H3(SiMe3)2-1,3}2(C6H6)] [Cp" = η5-C5H3(SiMe3)2-1,3; Ln = La, Ce, Nd] [J].

Cassani, MC ;

Gun'ko, YK ;

Hitchcock, PB ;

Lappert, MF ;

Laschi, F .

ORGANOMETALLICS, 1999, 18 (26) :5539-5547

[6] Heteroleptic Tm(II) complexes: One more success for Trofimenko's scorpionates [J].

Cheng, Jianhua ;

Takats, Josef ;

Ferguson, Michael J. ;

McDonald, Robert .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2008, 130 (05) :1544-+

[7] Synthesis, Structure, and Density Functional Theory Analysis of a Scandium Dinitrogen Complex, [(C5Me4H)2Sc]2(μ-η2:η2-N2) [J].

Demir, Selvan ;

Lorenz, Sara E. ;

Fang, Ming ;

Furche, Filipp ;

Meyer, Gerd ;

Ziller, Joseph W. ;

Evans, William J. .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2010, 132 (32) :11151-11158

[8] Tetrametallic divalent samarium cluster hydride and dinitrogen complexes [J].

Dubé, T ;

Ganesan, M ;

Conoci, S ;

Gambarotta, S ;

Yap, GPA .

ORGANOMETALLICS, 2000, 19 (18) :3716-3721

[9] X-Ray crystallographic and EPR spectroscopic characterization of a pyrrolidine adduct of Y3N@C80 [J].

Echegoyen, Luis ;

Chancellor, Christopher J. ;

Cardona, Claudia M. ;

Elliott, Bevan ;

Rivera, Jose ;

Olmstead, Marilyn M. ;

Balch, Alan L. .

CHEMICAL COMMUNICATIONS, 2006, (25) :2653-2655

[10] Synthesis, structure, and 15N NMR studies of paramagnetic lanthanide complexes obtained by reduction of dinitrogen [J].

Evans, William J. ;

Rego, Daniel B. ;

Ziller, Joseph W. .

INORGANIC CHEMISTRY, 2006, 45 (26) :10790-10798

← 1 2 3 4 5 →