Conversions of ruthenium(III) alkyl complexes to ruthenium(II) through Ru-Calkyl bond homolysis

被引：19

作者：

Lail, M

Gunnoe, TB

Barakat, KA

Cundari, TR

机构：

[1] N Carolina State Univ, Dept Chem, Raleigh, NC 27695 USA

[2] Univ N Texas, Dept Chem, Denton, TX 76203 USA

来源：

ORGANOMETALLICS | 2005年 / 24卷 / 06期

关键词：

D O I：

10.1021/om049145v

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

Single-electron oxidation of the Ru(II) complexes TpRu(L)(L')(R) (L = CO, L' = NCMe, and R = CH3 or CH2CH2Ph; L = L' = PMe3 and R = CH3) with AgOTf leads to alkyl elimination reactions that produce TpRu(L)(L')(OTf) and organic products that likely result from Ru-C-alkyl bond homolysis. Density functional calculations on TpRu(CO)(NCMe)(Me) and its Ru(III) cation indicate that the Ru-CH3 homolytic bond dissociation enthalpy is substantially reduced (48.6 to 23.2 kcal/mol) upon oxidation.

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页码：1301 / 1305

页数：5

相关论文

共 41 条

[1] INVOLVEMENT OF 19-ELECTRON SPECIES IN OXIDATIVELY INDUCED HOMOLYTIC METAL-CARBON BOND-CLEAVAGE REACTIONS - DECOMPOSITION OF 17-ELECTRON CYCLOPENTADIENYLRUTHENIUM METHYL CATIONS [J].

AASE, T ;

TILSET, M ;

PARKER, VD .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1990, 112 (12) :4974-4975

[2] Radical polymerization of styrene and methyl methacrylate with Ruthenium(II) complexes [J].

Arrowood, BN ;

Lail, M ;

Gunnoe, TB ;

Boyle, PD .

ORGANOMETALLICS, 2003, 22 (23) :4692-4698

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

BECKE, AD .

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

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

BECKE, AD .

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

[5] DENSITY-FUNCTIONAL EXCHANGE-ENERGY APPROXIMATION WITH CORRECT ASYMPTOTIC-BEHAVIOR [J].

BECKE, AD .

PHYSICAL REVIEW A, 1988, 38 (06) :3098-3100

[6] Computational study of methane activation by TpRe(CO)2 and CpRe(CO)2 with a stereoelectronic comparison of cyclopentadienyl and scorpionate ligands [J].

Bergman, RG ;

Cundari, TR ;

Gillespie, AM ;

Gunnoe, TB ;

Harman, WD ;

Klinckman, TR ;

Temple, MD ;

White, DP .

ORGANOMETALLICS, 2003, 22 (11) :2331-2337

[7] RADICAL MECHANISM FOR THE DECOMPOSITION OF RUOEP(CH2CH3)2 - DETERMINATION OF THE METAL-CARBON BOND-DISSOCIATION ENERGY [J].

COLLMAN, JP ;

MCELWEEWHITE, L ;

BROTHERS, PJ ;

ROSE, E .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1986, 108 (06) :1332-1333

[8] Synthesis and reactivity of a coordinatively unsaturated ruthenium(II) parent amido complex: Studies of X-H activation (X = H or C) [J].

Conner, D ;

Jayaprakash, KN ;

Cundari, TR ;

Gunnoe, TB .

ORGANOMETALLICS, 2004, 23 (11) :2724-2733

[9] Bimetallo-radical carbon-hydrogen bond activation of methanol and methane [J].

Cui, WH ;

Zhang, XP ;

Wayland, BB .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2003, 125 (17) :4994-4995

[10]

Frisch M.J., 2016, Gaussian 16 Revision C. 01. 2016, V01

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