A New Tripodal Ligand System with Steric and Electronic Modularity for Uranium Coordination Chemistry

被引:82
作者
Bart, Suzanne C. [1 ]
Heinemann, Frank W. [1 ]
Anthon, Christian [1 ]
Hauser, Christina [1 ]
Meyer, Karsten [1 ]
机构
[1] Univ Erlangen Nurnberg, Dept Chem & Pharm, D-91058 Erlangen, Germany
关键词
BIS(IMINO)PYRIDINE IRON; REDUCTIVE REACTIVITY; MOLECULAR-STRUCTURE; HYDRIDE COMPLEXES; CRYSTAL-STRUCTURE; CARBON-MONOXIDE; METAL-COMPLEXES; APPROXIMATION; ACTIVATION; ENERGY;
D O I
10.1021/ic9012697
中图分类号
O61 [无机化学];
学科分类号
070301 ; 081704 ;
摘要
The synthesis of a potentially redox active tripodal ligand containing a tris(aryloxide) functionalized mesitylene anchor, (((ArOH)-Ar-tBu)(3)mes) (1), and its metalation with low-valent uranium to form [(((ArO)-Ar-tBu)(3)mes)U] (1-U) is reported. The results from characterization by X-ray crystallography, spectroscopic studies, and computational analysis, as well as initial reactivity studies, support a +3 uranium oxidation state. Comparison to the previously synthesized complex, [(((ArO)-Ar-tBu)(3)tacn)U] (2-U), featuring the redox-innocent triazacyclononane anchor reveals that changing the anchor from the flexible triazacyclononane to a rigid mesityl fragment increases the structural flexibility of the aryloxide substituents in complexes of 1. The synthesis and crystal structures of uranium(IV) amide complexes of 1-U and 2-U are discussed.
引用
收藏
页码:9419 / 9426
页数:8
相关论文
共 54 条
[11]   Uranium tris-aryloxide derivatives supported by triazacyclononane: Engendering a reactive uranium(III) center with a single pocket for reactivity [J].
Castro-Rodriguez, I ;
Olsen, K ;
Gantzel, P ;
Meyer, K .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2003, 125 (15) :4565-4571
[12]   Uranium complexes supported by an aryloxide functionalised triazacyclononane macrocycle: synthesis and characterisation of a six-coordinate U(III) species and insights into its reactivity [J].
Castro-Rodriguez, I ;
Olsen, K ;
Gantzel, P ;
Meyer, K .
CHEMICAL COMMUNICATIONS, 2002, (23) :2764-2765
[13]  
DANOPOULOS AA, 2000, DALTON T, P1613
[14]  
DELPIERO G, 1975, CRYST STRUCT COMMUN, V4, P521
[15]   Arene-bridged diuranium complexes:: Inverted sandwiches supported by δ backbonding [J].
Diaconescu, PL ;
Arnold, PL ;
Baker, TA ;
Mindiola, DJ ;
Cummins, CC .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2000, 122 (25) :6108-6109
[16]   Diuranium inverted sandwiches involving naphthalene and cyclooctatetraene [J].
Diaconescu, PL ;
Cummins, CC .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2002, 124 (26) :7660-7661
[17]   The vitality of uranium molecular chemistry at the dawn of the XXIst century [J].
Ephritikhine, Michel .
DALTON TRANSACTIONS, 2006, (21) :2501-2516
[18]   Synthesis of (C5Me5)2(C5Me4H)UMe, (C5Me5)2(C5H5)UMe, and (C5Me5)2UMe[CH(SiMe3)2] from Cationic Metallocenes for the Evaluation of Sterically Induced Reduction [J].
Evans, William J. ;
Walensky, Justin R. ;
Furche, Filipp ;
Ziller, Joseph W. ;
DiPasquale, Antonio G. ;
Rheingold, Arnold L. .
INORGANIC CHEMISTRY, 2008, 47 (21) :10169-10176
[19]   Multi-electron reduction from alkyl/hydride ligand combinations in U4+ complexes [J].
Evans, William J. ;
Montalvo, Elizabeth ;
Kozimor, Stosh A. ;
Miller, Kevin A. .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2008, 130 (37) :12258-+
[20]   Reductive coupling of acetonitrile by uranium and thorium hydride complexes to give cyanopentadienyl dianion (C6N3H7)2- [J].
Evans, William J. ;
Miller, Kevin A. ;
Ziller, Joseph W. .
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2008, 47 (03) :589-592