Energetics of the ruthenium-halide bond in olefin metathesis (pre)catalysts

被引：36

作者：

Falivene, Laura ^{[1
]}

Poater, Albert ^{[2
,3
]}

Cazin, Catherine S. J. ^{[4
]}

Slugovc, Christian ^{[5
]}

Cavallo, Luigi ^{[1
,6
]}

机构：

[1] Univ Salerno, Dipartimento Chim & Biol, I-84084 Fisciano, Italy

[2] Univ Girona, Catalan Inst Water Res ICRA, E-17003 Girona, Spain

[3] Univ Girona, Dept Quim, Inst Quim Computac, E-17071 Girona, Spain

[4] Univ St Andrews, EaStCHEM Sch Chem, St Andrews KY16 9ST, Fife, Scotland

[5] Graz Univ Technol, Inst Chem & Technol Mat, A-8010 Graz, Austria

[6] KAUST, Kaust Catalysis Ctr, Thuwal 239556900, Saudi Arabia

来源：

DALTON TRANSACTIONS | 2013年 / 42卷 / 20期

关键词：

HETEROCYCLIC CARBENE LIGANDS; RING-CLOSING METATHESIS; GAUSSIAN-BASIS SETS; NONCOVALENT INTERACTIONS; MOLECULAR-INTERACTIONS; EFFICIENT CATALYSTS; COMPLEXES RELEVANT; ATOMS LI; GRUBBS; MECHANISM;

D O I：

10.1039/c2dt32277c

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

A DFT analysis of the strength of the Ru-halide bond in a series of typical olefin metathesis (pre)catalysts is presented. The calculated Ru-halide bond energies span the rather broad window of 25-43 kcal mol(-1). This indicates that in many systems dissociation of the Ru-halide bond is possible and is actually competitive with dissociation of the labile ligand generating the 14e active species. Consequently, formation of cationic Ru species in solution should be considered as a possible event.

引用

页码：7312 / 7317

页数：6

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