X-ray, 13C NMR, and DFT studies on a ruthenium(IV) allyl complex.: Explanation for the observed control of regioselectivity in allylic alkylation chemistry

被引：53

作者：

Hermatschweiler, R

Fernández, I

Pregosin, PS ^{[1
]}

Watson, EJ

Albinati, A

Rizzato, S

Veiros, LF

Calhorda, MJ

机构：

[1] ETH, HCI, Inorgan Chem Lab, CH-8093 Zurich, Switzerland

[2] Univ Milan, Dept Struct Chem, I-20133 Milan, Italy

[3] Inst Super Tecn, Ctr Quim Estrutural, P-1049001 Lisbon, Portugal

[4] Inst Tecnol Quim & Biol, P-2781901 Oeiras, Portugal

[5] Univ Lisbon, Dept Quim & Bioquim, Fac Ciencias, P-1749016 Lisbon, Portugal

来源：

ORGANOMETALLICS | 2005年 / 24卷 / 08期

关键词：

D O I：

10.1021/om049057a

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

X-ray, C-13 NMR, and DFT studies on the cationic Ru(IV) allyl complex Ru(Cp*)Cl(CH3CN)(eta(3)- PhCHCHCH2), as a PF6 salt, have revealed a marked asymmetry in the bonding of the allyl ligand, which can be interpreted as arising from differences in T-bonding from the metal center to the two terminal allyl carbons. This asymmetry in the bonding is offered as an explanation for the observed control of regioselectivity in the Ru-catalyzed allylic alkylation reaction.

引用

收藏

页码：1809 / 1812

页数：4

相关论文

共 23 条

[1] 1,3-DIPHENYLALLYL COMPLEXES OF PALLADIUM(II) - NMR, X-RAY, AND CATALYTIC STUDIES [J].

BARBARO, P ;

PREGOSIN, PS ;

SALZMANN, R ;

ALBINATI, A ;

KUNZ, RW .

ORGANOMETALLICS, 1995, 14 (11) :5160-5170

[2] Synthesis, characterization, and reactivity of half-sandwich Ru(II) complexes containing phosphine, arsine, stibine, and bismutine ligands [J].

Becker, E ;

Slugovc, C ;

Rüba, E ;

Standfest-Hauser, C ;

Mereiter, K ;

Schmid, R ;

Kirchner, K .

JOURNAL OF ORGANOMETALLIC CHEMISTRY, 2002, 649 (1-2) :55-63

[3] Synthesis and solid-state structure of [(η2:η5-C5Me4CH2CH2CH = CH2)Ru(η3-C3H5)] [J].

Castro, A ;

Turner, ML ;

Maitlis, PM .

JOURNAL OF ORGANOMETALLIC CHEMISTRY, 2003, 674 (1-2) :45-49

[4] Retention of regiochemistry of allylic esters in palladium-catalyzed allylic alkylation in the presence of a MOP ligand [J].

Hayashi, T ;

Kawatsura, M ;

Uozumi, Y .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1998, 120 (08) :1681-1687

[5] The first organoruthenium(IV) complexes containing nitrogen donor ligands by oxidative addition of allylic substrates to coordinatively unsaturated Ru(II) complexes [J].

Kondo, H ;

Yamaguchi, Y ;

Nagashima, H .

CHEMICAL COMMUNICATIONS, 2000, (12) :1075-1076

[6] Efficient synthesis of tris(acetonitrile)-(η5-cyclopentadienyl)ruthenium(II) hexafluorophosphate via ruthenocene [J].

Kündig, EP ;

Monnier, FR .

ADVANCED SYNTHESIS & CATALYSIS, 2004, 346 (08) :901-904

[7] Diastereoselective oxidative addition of allyl chloride to planar-chiral cyclopentadienyl-ruthenium complexes [J].

Matsushima, Y ;

Onitsuka, K ;

Takahashi, S .

ORGANOMETALLICS, 2004, 23 (16) :3763-3765

[8] Ruthenium-catalyzed O-allylation of phenols from allylic chlorides via cationic [Cp*(η3-allyl)(MeCN)RuX][PF6] complexes [J].

Mbaye, MD ;

Demerseman, B ;

Renaud, JL ;

Toupet, L ;

Bruneau, C .

ADVANCED SYNTHESIS & CATALYSIS, 2004, 346 (07) :835-841

[9] [Cp*(η2-bipy)(MeCN)RuII][PF6] catalysts for regioselective allylic substitution and characterization of dicationic [Cp*(η2-bipy)(η3-allyl)RuIV][PF6]2 intermediates [J].

Mbaye, MD ;

Demerseman, B ;

Renaud, JL ;

Toupet, L ;

Bruneau, C .

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2003, 42 (41) :5066-5068

[10] Ruthenium-catalyzed allylic substitution of cyclic allyl carbonates with nucleophiles. Stereoselectivity and scope of the reaction [J].

Morisaki, Y ;

Kondo, T ;

Mitsudo, TA .

ORGANOMETALLICS, 1999, 18 (23) :4742-4746