Facile C(sp2)/OR bond cleavage by Ru or Os

被引：26

作者：

Ferrando, G

Gérard, H

Spivak, GJ

Coalter, JN

Huffman, JC

Eisenstein, O ^{[1
]}

Caulton, KG

机构：

[1] Univ Montpellier 2, Lab Struct & Dynam & Syst Mol & Solides, UMR 5636, F-34095 Montpellier 5, France

[2] Indiana Univ, Dept Chem, Bloomington, IN 47405 USA

来源：

INORGANIC CHEMISTRY | 2001年 / 40卷 / 26期

关键词：

D O I：

10.1021/ic010729o

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

Os(H)(3)ClL2 (L = (PPr3)-Pr-i or (PBu2Me)-Bu-t) are shown to be useful "precursors" to "OsHClL2", which react with vinyl ethers to form first an eta (2)-olefin adduct and then isomerize to the carbenes, OsHCl[CMe(OR)]L-2. Subsequent Rand L-dependent reactions involve C(sp(2))-OR bond cleavage, to make either carbyne or vinylidene complexes. The mechanisms of these reactions are explored, and the thermodynamic disparity of Ru versus Os and the influence of the OR group and the spectator phosphine ligands are discussed based on DFT (B3PW91) calculations.

引用

收藏

页码：6610 / 6621

页数：12

相关论文

共 30 条

[1] DENSITY-FUNCTIONAL THERMOCHEMISTRY .3. THE ROLE OF EXACT EXCHANGE [J].

BECKE, AD .

JOURNAL OF CHEMICAL PHYSICS, 1993, 98 (07) :5648-5652

[2] The mechanism of the Ru-assisted C-C bond cleavage of terminal alkynes by water [J].

Bianchini, C ;

Casares, JA ;

Peruzzini, M ;

Romerosa, A ;

Zanobini, F .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1996, 118 (19) :4585-4594

[3] Reactions of new osmium-dihydride complexes with terminal alkynes:: Metallacyclopropene versus metal-carbyne.: Influence of the alkyne substituent [J].

Buil, ML ;

Eisenstein, O ;

Esteruelas, MA ;

García-Yebra, C ;

Gutiérrez-Puebla, E ;

Oliván, M ;

Oñate, E ;

Ruiz, N ;

Tajada, MA .

ORGANOMETALLICS, 1999, 18 (24) :4949-4959

[4] RUHX(H-2)((PPR3)-PR-I)(2) (X=CL, I) - 16-ELECTRON DIHYDROGEN-HYDRIDE OR TRIHYDRIDE COMPLEXES [J].

BURROW, T ;

SABOETIENNE, S ;

CHAUDRET, B .

INORGANIC CHEMISTRY, 1995, 34 (09) :2470-2472

[5] PREPARATION, X-RAY MOLECULAR-STRUCTURE, AND ELECTRONIC-STRUCTURE OF THE 1ST 16-ELECTRON DIHYDROGEN COMPLEXES RUH(H2)X(PCY3)2 [J].

CHAUDRET, B ;

CHUNG, G ;

EISENSTEIN, O ;

JACKSON, SA ;

LAHOZ, FJ ;

LOPEZ, JA .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1991, 113 (06) :2314-2316

[6] Carbene complexes from olefins, using RuHCl(PiPr3)2.: Influence of the olefin substituent [J].

Coalter, JN ;

Spivak, GJ ;

Gérard, H ;

Clot, E ;

Davidson, ER ;

Eisenstein, O ;

Caulton, KG .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1998, 120 (36) :9388-9389

[7] Coordinated carbenes from electron-rich olefins on RuHCl(PPri3)2 [J].

Coalter, JN ;

Bollinger, JC ;

Huffman, JC ;

Werner-Zwanziger, U ;

Caulton, KG ;

Davidson, ER ;

Gérard, H ;

Clot, E ;

Eisenstein, O .

NEW JOURNAL OF CHEMISTRY, 2000, 24 (01) :9-26

[8] SYNTHESIS OF NEW HYDRIDE-CARBYNE AND HYDRIDE-VINYLCARBYNE COMPLEXES OF OSMIUM(II) BY REACTION OF OSH2CL2(P-I-PR3)2 WITH TERMINAL ALKYNES [J].

ESPUELAS, J ;

ESTERUELAS, MA ;

LAHOZ, FJ ;

ORO, LA ;

RUIZ, N .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1993, 115 (11) :4683-4689

[9] 5-COORDINATE AND 6-COORDINATE HYDRIDO(CARBONYL)-RUTHENIUM(II) AND OSMIUM(II) COMPLEXES CONTAINING TRIISOPROPYLPHOSPHINE AS LIGAND [J].

ESTERUELAS, MA ;

WERNER, H .

JOURNAL OF ORGANOMETALLIC CHEMISTRY, 1986, 303 (02) :221-231

[10]

Frisch M.J., 2016, Gaussian 16 Revision C. 01. 2016, V16, P01