Ligand dissociation accelerated by spin state change:: locating the minimum energy crossing point for phosphine exchange in CpMoCl2(PR3)2 complexes

被引：55

作者：

Smith, KM

Poli, R

Harvey, JN

机构：

[1] Univ Bourgogne, Fac Sci, Lab Synth & Electrosynth Organomet, F-21100 Dijon, France

[2] Univ Bristol, Sch Chem, Bristol BS8 1TS, Avon, England

来源：

NEW JOURNAL OF CHEMISTRY | 2000年 / 24卷 / 02期

关键词：

D O I：

10.1039/a909646i

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

The minimum energy crossing point between the doublet and quartet potential energy surfaces of CpMoCl2(PH3)(2) is calculated to lie 4.8 kcal mol(-1) lower in energy than the doublet dissociative intermediate CpMoCl2(PH3). Implications for the influence of spin state changes on the rates of organometallic reactions are discussed.

引用

收藏

页码：77 / 80

页数：4

相关论文

共 48 条

[41] Hypersensitive mechanistic probe studies of cytochrome P450-catalyzed hydroxylation reactions. Implications for the cationic pathway [J].

Toy, PH ;

Newcomb, M ;

Hollenberg, PF .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1998, 120 (31) :7719-7729

[42] Reactions of ground-state Ti+ and V+ with propane:: Factors that govern C-H and C-C bond cleavage product branching ratios [J].

van Koppen, PAM ;

Bowers, MT ;

Haynes, CL ;

Armentrout, PB .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1998, 120 (23) :5704-5712

[43] Geometry of coordinatively unsaturated two-legged piano stool complexes with 16 valence electrons: A theoretical study [J].

Ward, TR ;

Schafer, O ;

Daul, C ;

Hofmann, P .

ORGANOMETALLICS, 1997, 16 (14) :3207-3215

[44] BARE TRANSITION-METAL ATOMS IN THE GAS-PHASE - REACTIONS OF M, M+, AND M2+ WITH HYDROCARBONS [J].

WEISSHAAR, JC .

ACCOUNTS OF CHEMICAL RESEARCH, 1993, 26 (04) :213-219

[45] Reaction mechanism of silicon-hydrogen bond activation studied using femtosecond to nanosecond IR spectroscopy and ab initio methods [J].

Yang, H ;

Asplund, MC ;

Kotz, KT ;

Wilkens, MJ ;

Frei, H ;

Harris, CB .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1998, 120 (39) :10154-10165

[46] SYSTEMATIC DETERMINATION OF INTERSECTIONS OF POTENTIAL-ENERGY SURFACES USING A LAGRANGE MULTIPLIER CONSTRAINED PROCEDURE [J].

YARKONY, DR .

JOURNAL OF PHYSICAL CHEMISTRY, 1993, 97 (17) :4407-4412

[47] Current issues in nonadiabatic chemistry [J].

Yarkony, DR .

JOURNAL OF PHYSICAL CHEMISTRY, 1996, 100 (48) :18612-18628

[48] On the mechanism of the spin-nonconserving chemical reaction O(3P)+HCCH→CH2((a)over-tilde1A1)+CO(X1Σ+).: I.: Feasibility [J].

Yarkony, DR .

JOURNAL OF PHYSICAL CHEMISTRY A, 1998, 102 (27) :5305-5311

← 1 2 3 4 5 →