Multi-electron reduction from alkyl/hydride ligand combinations in U4+ complexes

被引：53

作者：

Evans, William J. ^{[1
]}

Montalvo, Elizabeth ^{[1
]}

Kozimor, Stosh A. ^{[1
]}

Miller, Kevin A. ^{[1
]}

机构：

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

来源：

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY | 2008年 / 130卷 / 37期

基金：

美国国家科学基金会;

关键词：

D O I：

10.1021/ja805107v

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

The U4+ mixed alkyl hydride complex (C5Me5)U[mu-C5Me3(CH2)(2)] (mu-H)(2)U(C5M5)(2), 1, which contains a cyclopentadienyl ligand with two metalated methylene substituents, can effect four, six, and eight-electron reductions in which the combination of the two H1- ligands and the [C5Me3(CH2)(2)](3-) moiety delivers four electrons and forms (C5Me5)(1-). The reaction is formally equivalent to an alkyl hydride reductive elimination, a transformation common with transition metals not previously observed with f element compounds. This type of alkyl hydride reduction reactivity is also observed with a combination of U4+ alkyl and hydride complexes, (C5Me5)(2)UMe2/[(C5Me5)(2)UH2](2), which reduces benzene to make [(C5Me5)(2)U](2)(C6H6), a U3+ complex formally containing a (C6H6)(2-) ligand.

引用

页码：12258 / +

页数：3

共 28 条

[1] SYNTHESIS AND STRUCTURE OF THE 1ST URANIUM(VI) ORGANOMETALLIC COMPLEX [J].

ARNEY, DSJ ;

BURNS, CJ ;

SMITH, DC .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1992, 114 (25) :10068-10069

[2] Ring opening and C-O and C-N bond cleavage by transient reduced thorium species [J].

Arunachalampillai, Athimoolam ;

Crewdson, Patrick ;

Korobkov, Ilia ;

Gambarotta, Sandro .

ORGANOMETALLICS, 2006, 25 (16) :3856-3866

[3] Synthesis of a highly strained uranacycle: molecular structures of organometallic products arising from reduction, oxidation and protonolysis [J].

Boaretto, R ;

Roussel, P ;

Alcock, NW ;

Kingsley, AJ ;

Munslow, IJ ;

Sanders, CJ ;

Scott, P .

JOURNAL OF ORGANOMETALLIC CHEMISTRY, 1999, 591 (1-2) :174-184

[4] 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

[5] Synthesis, structure, and reactions of hydride, borohydride, and aluminohydride compounds of the f-elements [J].

Ephritikhine, M .

CHEMICAL REVIEWS, 1997, 97 (06) :2193-2242

[6] A crystallizable f-element tuck-in complex:: The tuck-in tuck-over uranium metallocene [(C5Me5)U{μ-η5:η1:η1-C5Me3(CH2)2}(μ-H)2U(C5Me5)2] [J].

Evans, William J. ;

Miller, Kevin A. ;

DiPasquale, Antonio G. ;

Rheingold, Arnold L. ;

Stewart, Timothy J. ;

Bau, Robert .

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2008, 47 (27) :5075-5078

[7] Two-electron reductive reactivity of trivalent uranium tetraphenylborate complexes of (C5Me5)1- and (C5Me4H)1- [J].

Evans, William J. ;

Miller, Kevin A. ;

Hillman, Wes R. ;

Ziller, Joseph W. .

JOURNAL OF ORGANOMETALLIC CHEMISTRY, 2007, 692 (17) :3649-3654

[8] Formation of (C5Me5)2U(EPh)Me, (C5Me5)2U(EPh)2, and (C5Me5)2U(η2-TeC6H4) from (C5Me5)2UMe2 and PhEEPh (E = S, Se, Te) [J].

Evans, William J. ;

Miller, Kevin A. ;

Ziller, Joseph W. ;

DiPasquale, Antonio G. ;

Heroux, Katie J. ;

Rheingold, Arnold L. .

ORGANOMETALLICS, 2007, 26 (17) :4287-4293

[9] Actinide hydride complexes as multielectron reductants:: Analogous reduction chemistry from [(C5Me5)2UH]2, [(C5Me5)2UH2]2, and [(C5Me5)2ThH2]2 [J].

Evans, William J. ;

Miller, Kevin A. ;

Kozimor, Stosh A. ;

Ziller, Joseph W. ;

DiPasquale, Antonio G. ;

Rheingold, Arnold L. .

ORGANOMETALLICS, 2007, 26 (14) :3568-3576

[10] Expanding the chemistry of U3+ reducing agents [J].

Evans, WJ ;

Kozimor, SA .

COORDINATION CHEMISTRY REVIEWS, 2006, 250 (7-8) :911-935

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