Reactivity of the tethered alkyl uranium bonds of (η5:κ1-C5Me4SiMe2CH2)2U

被引：26

作者：

Evans, William J. ^{[1
]}

Siladke, Nathan A. ^{[1
]}

Ziller, Joseph W. ^{[1
]}

机构：

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

来源：

COMPTES RENDUS CHIMIE | 2010年 / 13卷 / 6-7期

关键词：

Uranium; Cyclopentadienyl ligands; Insertion; Alkyl ligands; Metallocene; ACTINIDE-ALKYL; CARBON BONDS; COMPLEXES; INSERTION; CHEMISTRY; COORDINATION; LN;

D O I：

10.1016/j.crci.2010.02.003

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

Uranium-carbon bond reactivity has been investigated with the bis(tethered silylalkyl) uranium metallocene (eta(5).kappa(1)-C5Me4SiMe2CH2)(2)U, 1 Tert-butyl nitrile, (BuC)-Bu-t equivalent to N, inserts into both of the tethered U-C bonds to produce the bis(tethered ketimide) complex [eta(5).kappa(1)- C5Me4SiMe2CH2C(Bu-t)N](2)U, 2, which has unusually bent U-N-C bond angles Carbon dioxide also inserts Into both U-C bonds of 1 yielding the bis(tethered carboxylate) (C5Me4SiMe2CH2CO2)(2)U, 3. Neither PhC equivalent to CPh nor PhC=CH insert into the U-C bonds, but PhC equivalent to CH cleaves the silylalkyl tethers in 1 to generate (C5Me4SiMe3)(1-) ligands in the complex (C5Me4SiMe3)(2)U(CmCPh)(2), 4. (C) 2010 Academie des sciences. Published by Elsevier Masson SAS All rights reserved.

引用

页码：775 / 780

页数：6

共 28 条

[21] SYNTHESIS AND REACTIONS OF BIS(CYCLOPENTADIENYL)TITANIUM(IV) METALLOCYCLES [J].

MCDERMOTT, JX ;

WILSON, ME ;

WHITESIDES, GM .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1976, 98 (21) :6529-6536

[22] Trivalent lanthanide compounds with fluorinated thiolate ligands: Ln-F dative interactions vary with Ln and solvent [J].

Melman, JH ;

Rohde, C ;

Emge, TJ ;

Brennan, JG .

INORGANIC CHEMISTRY, 2002, 41 (01) :28-33

[23] THE INSERTION OF CARBON-DIOXIDE INTO ACTINIDE ALKYL AND HYDRIDE BONDS [J].

MOLOY, KG ;

MARKS, TJ .

INORGANICA CHIMICA ACTA-F-BLOCK ELEMENTS ARTICLES AND LETTERS, 1985, 110 (02) :127-131

[24] ACTINIDE-CARBON BONDS - INSERTION REACTIONS OF CARBON-MONOXIDE, TERT-BUTYL ISOCYANIDE, AND TERT-BUTYL CYANIDE INTO [(ME3SI)2N]2MCH2SI(ME)2NSIME3 [J].

SIMPSON, SJ ;

ANDERSEN, RA .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1981, 103 (14) :4063-4066

[25] SOLID-STATE STRUCTURE OF THE TANTALUM BIS-ARYL COMPOUNDS TA(OAR-2,6-R2)3(C6H5)2 (R=ME,ISO-PR-OAR-2,6-R2=2,6-DIALKYLPHENOXIDE) - OBSERVATION OF A LACK OF CORRELATION OF M-OAR DISTANCES AND M-O-AR ANGLES FOR ARYLOXIDE DERIVATIVES OF NIOBIUM(V) AND TANTALUM(V) [J].

STEFFEY, BD ;

FANWICK, PE ;

ROTHWELL, IP .

POLYHEDRON, 1990, 9 (07) :963-968

[26] Uranium(IV) bis(amido), imido and bis(acetylide) complexes: Synthesis, molecular structure, solution dynamics and interconversion reactions [J].

Straub, T ;

Frank, W ;

Reiss, GJ ;

Eisen, MS .

JOURNAL OF THE CHEMICAL SOCIETY-DALTON TRANSACTIONS, 1996, (12) :2541-2546

[27] Noble Reactions for the Actinides: Safe Gold-Based Access to Organouranium and Azido Complexes [J].

Thomson, Robert K. ;

Graves, Christopher R. ;

Scott, Brian L. ;

Kiplinger, Jaqueline L. .

EUROPEAN JOURNAL OF INORGANIC CHEMISTRY, 2009, (11) :1451-1455

[28] Cyclometalated phosphine-based pincer complexes: Mechanistic insight in catalysis, coordination, and bond activation [J].

van der Boom, ME ;

Milstein, D .

CHEMICAL REVIEWS, 2003, 103 (05) :1759-1792

← 1 2 3 →