Isolation and Characterization of a Tetramethyliron(III) Ferrate: An Intermediate in the Reduction Pathway of Ferric Salts with MeMgBr

被引：59

作者：

Al-Afyouni, Malik H. ^{[1
]}

Fillman, Kathlyn L. ^{[1
]}

Brennessel, William W. ^{[1
]}

Neidig, Michael L. ^{[1
]}

机构：

[1] Univ Rochester, Dept Chem, Rochester, NY 14627 USA

来源：

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY | 2014年 / 136卷 / 44期

基金：

美国国家卫生研究院;

关键词：

CROSS-COUPLING REACTIONS; ARYL GRIGNARD-REAGENTS; ALKYL-HALIDES; ALKENYL HALIDES; IRON CATALYSIS; ATE COMPLEX; REACTIVITY; OLEFINS;

D O I：

10.1021/ja5080757

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

While iron-catalyzed Kumada cross-coupling reactions with simple iron salts have been known since the early 1970s, the nature of the in situ-formed iron species remains elusive. Herein, we report the synthesis of the homoleptic tetralkyliron(III) ferrate complex [MgCl(THF)(5)][FeMe4] from the reaction of FeCl3 with MeMgBr in THF. Upon warming, this distorted square-planar S = (3)/(2) species converts to the S = (1)/(2) species originally observed by Kochi and co-workers with concomitant formation of ethane, consistent with its intermediacy in the reduction pathway of FeCl3 to generate the reduced iron species involved in catalysis.

引用

页码：15457 / 15460

页数：4

共 29 条

[1] The Cambridge Structural Database: a quarter of a million crystal structures and rising [J].

Allen, FH .

ACTA CRYSTALLOGRAPHICA SECTION B-STRUCTURAL SCIENCE, 2002, 58 (3 PART 1) :380-388

[2] A square-planar organoiron(III) compound with a spin-admixed state [J].

Alonso, Pablo J. ;

Arauzo, Ana B. ;

Fornies, Juan ;

Garcia-Monforte, M. Angeles ;

Martin, Antonio ;

Martinez, Jesus I. ;

Menjon, Babil ;

Rillo, Conrado ;

Saiz-Garitaonandia, Jose J. .

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2006, 45 (40) :6707-6711

[3] Iron-phosphine, -phosphite, -arsine, and -carbene catalysts for the coupling of primary and secondary 2 alkyl halides with aryl Grignard reagents [J].

Bedford, RB ;

Betham, M ;

Bruce, DW ;

Danopoulos, AA ;

Frost, RM ;

Hird, M .

JOURNAL OF ORGANIC CHEMISTRY, 2006, 71 (03) :1104-1110

[4] Expedient Iron-Catalyzed Coupling of Alkyl, Benzyl and Allyl Halides with Arylboronic Esters [J].

Bedford, Robin B. ;

Brenner, Peter B. ;

Carter, Emma ;

Carvell, Thomas W. ;

Cogswell, Paul M. ;

Gallagher, Timothy ;

Harvey, Jeremy N. ;

Murphy, Damien M. ;

Neeve, Emily C. ;

Nunn, Joshua ;

Pye, Dominic R. .

CHEMISTRY-A EUROPEAN JOURNAL, 2014, 20 (26) :7935-7938

[5] TMEDA in Iron-Catalyzed Kumada Coupling: Amine Adduct versus Homoleptic "ate" Complex Formation [J].

Bedford, Robin B. ;

Brenner, Peter B. ;

Carter, Emma ;

Cogswell, Paul M. ;

Haddow, Mairi F. ;

Harvey, Jeremy N. ;

Murphy, Damien M. ;

Nunn, Joshua ;

Woodall, Christopher H. .

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2014, 53 (07) :1804-1808

[6] FORMATION OF LITHIUM TETRACHLOROFERRATE(II), LI2FECL4, ON REACTION OF IRON(III) CHLORIDE AND METHYL LITHIUM IN ETHERIC SOLUTION [J].

BERTHOLD, HJ ;

SPIEGL, HJ .

ZEITSCHRIFT FUR ANORGANISCHE UND ALLGEMEINE CHEMIE, 1972, 391 (03) :193-&

[7] Iron-catalyzed reactions in organic synthesis [J].

Bolm, C ;

Legros, J ;

Le Paih, J ;

Zani, L .

CHEMICAL REVIEWS, 2004, 104 (12) :6217-6254

[8] VTVH-MCD and DFT studies of thiolate bonding to {FeNO}7/{FeO2}8 complexes of isopenicillin N synthase:: Substrate determination of oxidase versus oxygenase activity in nonheme Fe enzymes [J].

Brown, Christina D. ;

Neidig, Michael L. ;

Neibergall, Matthew B. ;

Lipscomb, John D. ;

Solomon, Edward I. .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2007, 129 (23) :7427-7438

[9]

Cahiez G, 1998, SYNTHESIS-STUTTGART, P1199

[10] S=3/2 ⇆ S=1/2 spin crossover behavior in five-coordinate halido- and pseudohalido-bis(o-iminobenzosemiquinonato)iron(III) complexes [J].

Chun, HP ;

Bill, E ;

Weyhermuller, T ;

Wieghardt, K .

INORGANIC CHEMISTRY, 2003, 42 (18) :5612-5620

← 1 2 3 →