Photochemical C-H bond activation of the diruthenium bridging methylene complex, Cp2Ru2(μ-CH2)2(CO)2:: insertion of norbornadienes into the methylene C-H bond and unprecedented intramolecular H-D exchange between the two methylene units

被引：3

作者：

Akita, M ^{[1
]}

Nakanishi, S ^{[1
]}

Musashi, H ^{[1
]}

Moro-oka, Y ^{[1
]}

机构：

[1] Tokyo Inst Technol, Resources Utilizat Res Lab, Midori Ku, Yokohama, Kanagawa 2268503, Japan

来源：

CHEMICAL COMMUNICATIONS | 1999年 / 02期

关键词：

D O I：

10.1039/a808411d

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

Two photochemical reactions of the diruthenium bis-mu-methhylene complex (eta(5)-(CH5)-H-5)(2)Ru-2(mu-CH2)(2)(CO)(2) are described: (i) insertion reaction of norbornadiene into the methylene C-H bonds leading to (eta(5)-C5H5)(2)Ru-2(mu-CHR')(2)(CO)(2) (R' = 5-exo-norbornenyl) and (ii) H exchange between the two methylene units, involve p-methylidyne intermediates generated via C-H band activation of the mu-methylene ligand.

引用

页码：145 / 146

页数：2

共 16 条

[1] Specific C-C coupling of the labile diruthenium bridging methylene complex, Cp2Ru2(μ-CH2)(CO)2(MeCN), with diazoalkanes (R2C=N2) leading to alkenyl complexes, Cp2Ru2(μ-CH=CR2)(μ-H)(CO)2, and alkenes, CH2=CR2 [J].

Akita, M ;

Hua, R ;

Knox, SAR ;

Moro-oka, Y ;

Nakanishi, S ;

Yates, MI .

JOURNAL OF ORGANOMETALLIC CHEMISTRY, 1998, 569 (1-2) :71-83

[2] Deoxygenative reduction of diruthenium carbonyl complexes (eta(5)-C(5)H(4)R)(2)Ru-2(mu-CO)(2)(CO)(2) with hydrosilanes leading to bridging methylene complexes (eta(5)-C(5)H(4)R)(2)Ru-2(mu-CH2)(n)(mu-CO)(2-n)(CO)(2) (n=1, 2; R=H, CH3) [J].

Akita, M ;

Hua, RM ;

Oku, T ;

Morooka, Y .

ORGANOMETALLICS, 1996, 15 (10) :2548-2553

[3] Conversion of a diruthenium mu-methylene complex, Cp(2)Ru(2)(mu-CH2)(mu-CO)(CO)(2), into methane through reduction with hydrosilane: Reactivity of silyl-mu-methylene intermediates Cp(2)Ru(2)(mu-CH2)(SiR(3))(X)(CO)(2) (X=H, SiR(3)) relevant to catalytic CO hydrogenation and activation of Si-H, C-H, and C-Si bonds [J].

Akita, M ;

Hua, R ;

Oku, T ;

Tanaka, M ;

MoroOka, Y .

ORGANOMETALLICS, 1996, 15 (20) :4162-4177

[4] Synthesis and reactivity of labile MeCN adducts of diruthenium bis(mu-methylene) species, Cp2Ru2(mu-CH2)(2)(CO)(n)(MeCN)(2-n) (n = 1, 2): Reaction with H sources, H-X (X = SiR3, SnR3, H), and C-C coupling with alkynes and diazoalkanes [J].

Akita, M ;

Hua, R ;

Nakanishi, S ;

Tanaka, M ;

Morooka, Y .

ORGANOMETALLICS, 1997, 16 (25) :5572-5584

[5]

AKITA M, UNPUB

[6] REACTIONS OF A CATIONIC BRIDGING METHYLIDYNE IRON COMPLEX WITH CARBON-MONOXIDE AND WITH ALKENES [J].

CASEY, CP ;

FAGAN, PJ ;

MILES, WH ;

MARDER, SR .

JOURNAL OF MOLECULAR CATALYSIS, 1983, 21 (OCT) :173-188

[7] HYDROCARBATION - ADDITION OF THE C-H BOND OF A CATIONIC BRIDGING IRON METHYLIDYNE COMPLEX TO ALKENES [J].

CASEY, CP ;

FAGAN, PJ .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1982, 104 (18) :4950-4951

[8] SYNTHESIS AND INTERCONVERSIONS OF DINUCLEAR IRON COMPLEXES WITH MU-CH3, MU-CH2, AND MU-CH LIGANDS [J].

CASEY, CP ;

FAGAN, PJ ;

MILES, WH .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1982, 104 (04) :1134-1136

[9] ACTIVATION OF MU-ALKYLIDENE LIGANDS THROUGH OXIDATION-DEPROTONATION - A NEW SYNTHESIS OF MU-METHYNE, AND ITS HYDROGENATION TO MU-METHYL [J].

CONNELLY, NG ;

FORROW, NJ ;

GRACEY, BP ;

KNOX, SAR ;

ORPEN, AG .

JOURNAL OF THE CHEMICAL SOCIETY-CHEMICAL COMMUNICATIONS, 1985, (01) :14-16

[10] METHYL-GROUP MOBILITY AND CONVERSION INTO METHYNE AT A DIRUTHENIUM CENTER [J].

DAVIES, DL ;

GRACEY, BP ;

GUERCHAIS, V ;

KNOX, SAR ;

ORPEN, AG .

JOURNAL OF THE CHEMICAL SOCIETY-CHEMICAL COMMUNICATIONS, 1984, (13) :841-843

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