Syntheses of acyl rhodium porphyrins by aldehydic carbon-hydrogen bond activation with Rh(III) porphyrin chloride and methyl

被引：40

作者：

Chan, KS ^{[1
]}

Lau, CM ^{[1
]}

机构：

[1] Chinese Univ Hong Kong, Dept Chem, Shatin, Hong Kong, Peoples R China

来源：

ORGANOMETALLICS | 2006年 / 25卷 / 01期

关键词：

D O I：

10.1021/om0507878

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

Rhodium(III) porphyrin chloride reacted with aryl aldehydes in solvent-free conditions to give acyl rhodium porphyrins. Selective aldehydic without any aromatic carbon-hydrogen bond activation (CHA) was observed. At lower temperature, reduction and side products were found. Alkanals reacted poorly. On the other hand, Rh(III) porphyrin methyl reacted more cleanly with both aryl and alkyl aldehydes. These reactions provided a facile, convenient synthesis of acyl rhodium porphyrins. These activations are unique CHA by high-valent Rh(III) species. Preliminary mechanistic experiments suggested that the rhodium(III) porphyrin chloride initially formed a cationic rhodium(III) porphyrin via chloride dissociation and then underwent oxidative addition or heterolysis to yield the product. On the other hand, rhodium(Ill) porphyrin methyl underwent either oxidative addition or a bond metathesis.

引用

页码：260 / 265

页数：6

共 31 条

[11] The mechanism of silicon-hydrogen and carbon-hydrogen bond activation by iridium(III): Production of a silylene complex and the first direct observation of Ir(III)/Ir(V) C-H bond oxidative addition and reductive elimination [J].

Klei, SR ;

Tilley, TD ;

Bergman, RG .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2000, 122 (08) :1816-1817

[12] Understanding and exploiting C-H bond activation [J].

Labinger, JA ;

Bercaw, JE .

NATURE, 2002, 417 (6888) :507-514

[13] Mechanistic aspects of C-H activation by Pt complexes [J].

Lersch, M ;

Tilset, M .

CHEMICAL REVIEWS, 2005, 105 (06) :2471-2526

[14] Catalytic Shilov chemistry: Platinum chloride-catalyzed oxidation of terminal methyl groups by dioxygen [J].

Lin, MR ;

Shen, CY ;

Garcia-Zayas, EA ;

Sen, A .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2001, 123 (05) :1000-1001

[15] TRANSITION-METAL-CATALYZED C-C BOND FORMATION VIA C-H ACTIVATION - INTERMOLECULAR HYDROACYLATION - THE ADDITION OF ALDEHYDES TO ALKENES [J].

MARDER, TB ;

ROE, DC ;

MILSTEIN, D .

ORGANOMETALLICS, 1988, 7 (06) :1451-1453

[16] CIS-HYDRIDOACYLRHODIUM(III) COMPLEXES NOT STABILIZED BY CHELATION - REDUCTIVE ELIMINATION AND DECARBONYLATION [J].

MILSTEIN, D .

ORGANOMETALLICS, 1982, 1 (11) :1549-1551

[17] NOVEL RHODIUM(I)-PORPHYRIN COMPLEXES AND ORGANORHODIUM(III)-PORPHYRIN COMPLEXES .4. [J].

OGOSHI, H ;

SETSUNE, J ;

OMURA, T ;

YOSHIDA, Z .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1975, 97 (22) :6461-6466

[18] Catalytic, oxidative condensation of CH4 to CH3COOH in one step via CH activation [J].

Periana, RA ;

Mironov, O ;

Taube, D ;

Bhalla, G ;

Jones, CJ .

SCIENCE, 2003, 301 (5634) :814-818

[19] Platinum catalysts for the high-yield oxidation of methane to a methanol derivative [J].

Periana, RA ;

Taube, DJ ;

Gamble, S ;

Taube, H ;

Satoh, T ;

Fujii, H .

SCIENCE, 1998, 280 (5363) :560-564

[20] REACTIONS OF ISOCYANIDES WITH RHODIUM PORPHYRINS - FORMATION OF FORMIMIDOYL AND CARBAMOYL COMPLEXES AND CN-R BOND-CLEAVAGE [J].

POSZMIK, G ;

CARROLL, PJ ;

WAYLAND, BB .

ORGANOMETALLICS, 1993, 12 (09) :3410-3417

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