7245-25-2Relevant academic research and scientific papers
New insights into the mechanism of iron-catalyzed cross-coupling reactions
Bekhradnia, Ahmadreza,Norrby, Per-Ola
, p. 3959 - 3962 (2015)
The mechanism of the iron-catalyzed cross-coupling of alkyl halides with aryl Grignard reagents is studied by a combination of GC monitoring and DFT calculation. Herein, we investigate two possible reaction pathways, the regular oxidative addition (OA) pathway and the atom transfer (AT) pathway that might occur in the rate-limiting step. The computational studies revealed that the AT pathway requires less energy than the regular OA pathway.
Alcoholysis of [Fe2(OtBu)6] as a simple route to new iron(III)-alkoxo compounds: Synthesis and crystal structures of (2), (3), (4), (5), (6), (7), and (8)
Kusserow,Spandl
, p. 885 - 892 (2008/10/09)
New alkoxo-iron compounds can be synthesized easily by alcoholysis of [Fe2(OtBu)6] (1). Due to different bulkyness of the alcohols used, three different structure types are formed: [Fe 2(OR)6], [Fe5O(OR)13] and [Fe 9O3(OR)21]·ROH. We report synthesis and crystal structures of the compounds [Fe5OCl(OiPr) 12] (2), [Fe2(OtAmyl)6] (3), [Fe5O(OiPr)13] (4), [Fe5O(O iBu)13] (5), [Fe5O(OCH2CF 3)13] (6), [Fe9O3(O nPr)21] · nPrOH (7) and [Fe 5O(OnPr)13] (8). Cryslallographic Data: 2, tetragonal, P 4/n, a = 16.070(5) A, c = 9.831(5) A, V = 2539(2) A3, Z = 2, dc = 1.360 gcm-3, R 1 = 0.0636; 3, monoclinic, P 21/c, a = 10.591(5) A, b = 10.654(4) A, c = 16.740(7) A, β = 104.87(2)°, V = 1826(2) A3, Z = 2, dc = 1.154 gcm-3, R1 = 0.0756; 4, triclinic, P 1, a = 20.640(3) A, b = 21.383(3) A, c = 21.537(3) A, a = 82.37(1)°, β = 73.15(1)°, γ = 61.75(1)°, V = 8013(2) A3, Z = 6, dc = 1.322 gcm-3, R1 = 0.0412; 5, tetragonal, P 4cc, a = 13.612(5) A, c = 36.853(5) A, V = 6828(4) A3, Z = 4, dc = 1.079 gcm-3, R1 = 0.0609; 6, triclinic, P 1, a = 12.039(2) A, b = 12.673(3) A, c = 19.600(4) A, a = 93.60(1)°, β = 97.02(1)°, γ = 117.83(1)°, V = 2600(2) A3, Z = 2, dc = 2.022 gcm-3, R 1 = 0.0585; 7, triclinic, P 1, a = 12.989(3) A, b = 16.750(4) A, c = 21.644(5) A, α = 84.69(1)°, β = 86.20(1)°, γ = 77.68(1)°, V = 4576(2) A3, Z = 2, dc = 1.344 gcm-3, R1 = 0.0778; 8, triclinic, P 1, a = 12.597(5) A, b = 12.764(5) A, c = 16.727(7) A, α = 91.94(1)°, β = 95.61(1)°, γ = 93.24(2)°, V = 2670(2) A3, Z = 2, dc = 1.323 gcm-3, R 1 = 0.0594.
Transition Metal Alkoxides. Preparation and Properties of Bis(aryloxo)iron(II) and Bis(alkoxo)iron(II) Complexes Having 2,2'-Bipyridine Ligands
Komiya, Sanshiro,Tane-ichi, Shoshiro,Yamamoto, Akio,Yamamoto, Takakazu
, p. 673 - 679 (2007/10/02)
A series of bis(aryloxo)iron(II), 2a-2g, and bis(alkoxo)iron(II), 2h-2k, complexes with 2,2'-bipyridine ligands (Fe()C6H4X)2(bpy)n and Fe(OR)2(bpy)n) have been prepared by the reactions of diethylbis(2,2'-bipyridine)iron(II) (1) with corresponding p-substituted phenols and alcohols, respectively. (X = NO2, CN, Cl, C6H5, H, and CH3; R = CH3, C2H5, iso-C3H7, and CH2C6H5).These compounds were characterized by IR and NMR spectroscopies and elemental analyses as well as by chemical reactions.Kinetic investigation of the reactions of 1 with phenols by a visible spectroscopic method supports a mechanism involving partial dissociation of the 2,2'-bipyridine ligand, followed by coordination of phenol and activation of the Fe-C2H5 bonds giving the bis(phenoxo)iron(II) compound.Thermolysis of bis(alkoxo)iron(II) complexes give not only disproportionation products of the alkoxo ligands (alcohols and aldehydes) but also organic products which are obtained as the result of C-O bond cleavage of the alkoxo groups.Interactions of 2 with acyl and alkyl halides lead to the formation of corresponding esters and ethers.Reactions of these iron(II) complexes with various organic acetates give corresponding acetates via an alkoxo exchange reaction.Bis(aryloxo)iron(II) complexes, 2, are hydrolyzed with H2O to yield phenols.Catalytic trans-esterification between ester and alcohol and Tishchenko type dimerization of benzaldehyde are effectively promoted under mild conditions by the bis(phenoxo)iron(II) and bis(benzyloxo)iron(II) complexes, respectively.
