An Alkali Metal-Capped Cerium(IV) Imido Complex

被引：65

作者：

Solola, Lukman A. ^{[1
]}

Zabula, Alexander V. ^{[1
]}

Dorfner, Walter L. ^{[1
]}

Manor, Brian C. ^{[1
]}

Carroll, Patrick J. ^{[1
]}

Schelter, Eric J. ^{[1
]}

机构：

[1] Univ Penn, Dept Chem, P Roy & Diana T Vagelos Labs, 231 South 34th St, Philadelphia, PA 19104 USA

来源：

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY | 2016年 / 138卷 / 22期

基金：

美国国家科学基金会;

关键词：

PHOSPHINIDENE COMPLEXES; URANIUM; CHEMISTRY; TITANIUM; REACTIVITY; ELEMENTS; NITRIDE; OXO;

D O I：

10.1021/jacs.6b03293

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

Structurally authenticated, terminal lanthanide-ligand multiple bonds are rare and,expected to be highly reactive. Even capped with an alkali metal cation, poor orbital energy matching and. overlap of metal and ligand valence orbitals should result in strong charge polarization within such bonds. We expand on a new strategy for isolating terminal lanthanide-ligand multiple bonds using cerium(IV) complexes In the Current,case, our tailored tris(hydroxylaminato), ligand framework, TriNOx(3-), provides steric protection against ligand scrambling and. metal complex oligomerization and electronic protection against reduction. This strategy culminates in isolation of the first formal Ce=N bonded moiety in the complex [K(DME)(2)][Ce=N(3,5-(CF3)(2)C6H3)(TriNOx)], whose Ce=N bond is the shortest known at 2.119(3) angstrom.

引用

页码：6928 / 6931

页数：4

共 39 条

[1] Nucleophilic Phosphinidene Complexes: Access and Applicability [J].

Aktas, Halil ;

Slootweg, J. Chris ;

Lammertsma, Koop .

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2010, 49 (12) :2102-2113

[2] Investigation of Uranium Tris(imido) Complexes: Synthesis, Characterization, and Reduction Chemistry of [U(NDIPP)3(thf)3] [J].

Anderson, Nickolas H. ;

Yin, Haolin ;

Kiernicki, John J. ;

Fanwick, Phillip E. ;

Schelter, Eric J. ;

Bart, Suzanne C. .

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2015, 54 (32) :9386-9389

[3]

Anderson NH, 2014, NAT CHEM, V6, P919, DOI [10.1038/nchem.2009, 10.1038/NCHEM.2009]

[4] Carbon dioxide activation with sterically pressured mid- and high-valent uranium complexes [J].

Bart, Suzanne C. ;

Anthon, Christian ;

Heinemann, Frank W. ;

Bill, Eckhard ;

Edelstein, Norman M. ;

Meyer, Karsten .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2008, 130 (37) :12536-12546

[5] A terminal and four-coordinate titanium alkylidene prepared by oxidatively induced α-hydrogen abstraction [J].

Basuli, F ;

Bailey, BC ;

Tomaszewski, J ;

Huffman, JC ;

Mindiola, DJ .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2003, 125 (20) :6052-6053

[6] Formation of a Bridging Phosphinidene Thorium Complex [J].

Behrle, Andrew C. ;

Castro, Ludovic ;

Maron, Laurent ;

Walensky, Justin R. .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2015, 137 (47) :14846-14849

[7] Controlled Redox Chemistry at Cerium within a Tripodal Nitroxide Ligand Framework [J].

Bogart, Justin A. ;

Lippincott, Connor A. ;

Carroll, Patrick J. ;

Booth, Corwin H. ;

Schelter, Eric J. .

CHEMISTRY-A EUROPEAN JOURNAL, 2015, 21 (49) :17850-17859

[8] An Operationally Simple Method for Separating the Rare-Earth Elements Neodymium and Dysprosium [J].

Bogart, Justin A. ;

Lippincott, Connor A. ;

Carroll, Patrick J. ;

Schelter, Eric J. .

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2015, 54 (28) :8222-8225

[9] Homoleptic Cerium(III) and Cerium(IV) Nitroxide Complexes: Significant Stabilization of the 4+Oxidation State [J].

Bogart, Justin A. ;

Lewis, Andrew J. ;

Medling, Scott A. ;

Piro, Nicholas A. ;

Carroll, Patrick J. ;

Booth, Corwin H. ;

Schelter, Eric J. .

INORGANIC CHEMISTRY, 2013, 52 (19) :11600-11607

[10] Synthesis and structural characterization of imido-lanthanide complexes with a metal-nitrogen multiple bond [J].

Chan, HS ;

Li, HW ;

Xie, ZW .

CHEMICAL COMMUNICATIONS, 2002, (06) :652-653

← 1 2 3 4 →