Structure of the intermediate iron(0) complex isolated from the dinitrogen fixing system LiPh + FeCl3

Bazhenova, T. A.; Lobkovskaya, R. M.; Shibaeva, R. P.; Шилов, А. Е.; Shilova, A. K.; Gruselle, Michel; Leny, G.; Tchoubar, B.

doi:10.1016/s0022-328x(00)98618-2

Cited by 43 publications

(22 citation statements)

References 3 publications

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“…Notably, a homoleptic Fe(0) ferrate species [Ph 4 Fe(0)][Li(OEt 2 )] 4 , prepared from the reaction of FeCl 3 with excess PhLi in Et 2 O at low temperature, has been isolated and characterized by X-ray crystallography, and shown to be active in the reduction of N 2 , possibly by pre-complexation of the π-acceptor N 2 molecule to the iron center. 83 Following the generation of the catalytically active Fe(0)(aryl) n ferrate species 31 , coordination of the thio ether substrate 3d through the pyridyl nitrogen atom may give adduct 32 . Oxidative addition of the C(sp 3 )–S bond to the iron center ( vide infra ) could then generate Fe(II) species 33 , which would suffer reductive elimination to afford the product 34 and furnish an Fe(0)(aryl) n–1 species 35 .…”

Section: Discussionmentioning

confidence: 99%

Iron-Catalyzed Cross-Coupling of Unactivated Secondary Alkyl Thio Ethers and Sulfones with Aryl Grignard Reagents

2013

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The first systematic investigation of unactivated aliphatic sulfur compounds as electrophiles in transition metal-catalyzed cross-coupling are described. Initial studies focused on discerning the structural and electronic features of the organosulfur substrate which enable the challenging oxidative addition to the C(sp3)–S bond. Through extensive optimization efforts, an Fe(acac)3-catalyzed cross-coupling of unactivated alkyl aryl thio ethers with aryl Grignard reagents was realized, in which a nitrogen “directing group” on the S-aryl moiety of the thio ether served a critical role in facilitating the oxidative addition step. In addition, alkyl phenyl sulfones were found to be effective electrophiles in the Fe(acac)3-catalyzed cross-coupling with aryl Grignard reagents. For the latter class of electrophile, a thorough assessment of the various reaction parameters revealed a dramatic enhancement in reaction efficiency with an excess of TMEDA (8.0 equiv). The optimized reaction protocol was used to evaluate the scope of the method with respect to both the organomagnesium nucleophile and sulfone electrophile.

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Section: Discussionmentioning

confidence: 99%

Iron-Catalyzed Cross-Coupling of Unactivated Secondary Alkyl Thio Ethers and Sulfones with Aryl Grignard Reagents

2013

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“…The structure reported for [FePh 4 ] 4À seems to have a severe scissoring distortion (C-Fe-C bond angles of 618), [120] but later structural redeterminations [121,122] of that compound found the Fe atom to be hexacoordinate with regular bond angles of 908, corresponding to the formula [FeH 2 Ph 4 ] 4À . Although statistically of little significance, a few sawhorse structures have beeen identified, such as the Ir I and Ru 0 compounds presented in Table 2.…”

Section: Distribution Of Experimental Tetracoordinate Structuresmentioning

confidence: 99%

Mapping the Stereochemistry and Symmetry of Tetracoordinate Transition‐Metal Complexes

Cirera

Alemany

Álvarez

2003

Chemistry A European J

198

203

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A continuous shape and symmetry study of tetracoordinate transition-metal complexes is presented, in an attempt to provide a systematic description of the stereochemistry of the metal coordination sphere in this important family of compounds. A tetrahedron/square-planar symmetry map has been developed, the main distortion paths of the ideal geometries are presented, and the applicability of a sawhorse shape measure is discussed. More than 13,000 structural data sets have been analyzed and the corresponding stereochemistries assigned from the values of their tetrahedral and square-planar symmetry measures. A good number of structures that are quite distant from the two ideal geometries can be adequately described as snapshots along the spread pathway for their interconversion, making use of the corresponding path deviation function. Further analysis of the structural data by metal electron configuration or by the denticity and conformation of the ligands provide general rules to describe the stereochemical preferences of tetracoordinate transition metal centers.

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“…Three of the clusters are black FeLU [84,85]. In two of them, [Ρβ(μ 3 -ί) 4 Structure of yellow FeMg 4 complex [86] is shown in Fig.…”

Section: -Non -Transition Elements μmentioning

confidence: 99%

Crystallographic and Structural Analysis of Iron Heterometallic Compounds Part IV: Heteropentameric Compounds

Melnı́k¹,

Ondrejkovičová²,

Koman³

2010

Reviews in Inorganic Chemistry

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Structure of the intermediate iron(0) complex isolated from the dinitrogen fixing system LiPh + FeCl3

Cited by 43 publications

References 3 publications

Iron-Catalyzed Cross-Coupling of Unactivated Secondary Alkyl Thio Ethers and Sulfones with Aryl Grignard Reagents

Iron-Catalyzed Cross-Coupling of Unactivated Secondary Alkyl Thio Ethers and Sulfones with Aryl Grignard Reagents

Mapping the Stereochemistry and Symmetry of Tetracoordinate Transition‐Metal Complexes

Crystallographic and Structural Analysis of Iron Heterometallic Compounds Part IV: Heteropentameric Compounds

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