850131-89-4Relevant academic research and scientific papers
Direct Observation of Transmetalation from a Neutral Boronate Ester to a Pyridine(diimine) Iron Alkoxide
Chirik, Paul J.,Peterson, Paul O.,Rummelt, Stephan M.,Stieber, S. Chantal E.,Wile, Bradley M.,Zhong, Hongyu
, (2020)
Transmetalation of the neutral boronate esters, (2-benzofuranyl)BPin and (2-benzofuranyl)BNeo (Pin = pinacolato, Neo = neopentylglycolato), to a representative pyridine(diimine) iron alkoxide complex, (iPrPDI)FeOEt (iPrPDI = 2,6-(2,6-iPr2-C6H3Na? CMe)2C5H3N; R = Me, Et, SiMe3), to yield the corresponding iron benzofuranyl derivative was studied. Synthesis of the requisite iron alkoxide complexes was accomplished either by salt metathesis between (iPrPDI)FeCl and NaOR (R = Me, Et, SiMe3) or by protonation of the iron alkyl, (iPrPDI)FeCH2SiMe3, by the free alcohol R′OH (R′ = Me, Et). A combination of magnetic measurements, X-ray diffraction, NMR, and M?ssbauer spectroscopies and DFT calculations identified each (iPrPDI)FeOR compound as an essentially planar, high-spin, S = 3/2 compound where the iron is engaged in antiferromagnetic coupling with a radical anion on the chelate (STotal = 3/2; SFe = 2, SPDI =-1/2). The resulting iron benzofuranyl product, (iPrPDI)Fe(2-benzofuranyl), was characterized by X-ray diffraction and in combination with magnetic measurements, spectroscopic and computational data, was identified as an overall S = 1/2 compound, demonstrating that a net spin-state change accompanies transmetalation (SFe = 1, SPDI =-1/2). These findings may be relevant to further development of iron-catalyzed Suzuki-Miyaura cross-coupling with neutral boronate esters and alkoxide bases.
Synthesis of iron(II), manganese(II), cobalt(II) and ruthenium(II) complexes containing tridentate nitrogen ligands and their application in the catalytic oxidation of alkanes
Britovsek, George J. P.,England, Jason,Spitzmesser, Stefan K.,White, Andrew J.P.,Williams, David J.
, p. 945 - 955 (2007/10/03)
A series of Fe(II), Mn(II), Co(II) and Ru(II) complexes containing bis(imino) pyridine or bis(amino)pyridine ligands and weakly coordinating triflate (OTf-) or non-coordinating SbF6- anions have been prepared. The complexes have been fully characterized including several solid-state structure analyses. Two unusual mono-chelate six-coordinate bis(imino)pyridine Fe(II) and Mn(II) complexes have been observed. The catalytic properties of the complexes for the oxidation of cyclohexane with H2O2 have been evaluated. Only the Fe(II) complexes have shown catalytic activity, which is mainly due to Fenton-type free radical auto-oxidation. The Royal Society of Chemistry 2005.
