658063-27-5Relevant academic research and scientific papers
Low-valent α-diimine iron complexes for catalytic olefin hydrogenation
Bart, Suzanne C.,Hawrelak, Eric J.,Lobkovsky, Emil,Chirik, Paul J.
, p. 5518 - 5527 (2008/10/09)
A family of low-valent α-diimine iron complexes has been synthesized and their utility in catalytic olefin hydrogenation reactions evaluated. Reduction of the ferrous dichloride complex [ArN=C(Me)C(Me)=NAr]FeCl2 (Ar = 2,6-(CHMe2)2-C6H3) with sodium amalgam in benzene or toluene furnished the iron arene complexes, [ArN=C(Me)C(Me)=NAr]Fe(η6-C6H5R) (R = H, Me). The solid-state structure of the toluene adduct revealed a contracted carbon-carbon backbone, short iron-imine bonds, and elongated imine nitrogen-carbon distances, suggesting significant reduction of the α-diimine ligand. The analogous reduction in alkane solvents afforded the bis(α-diimine) complex [ArN=C(Me)C(Me)=NAr]2Fe, which has also been crystallographically characterized. The arene complexes and the bis(a-diimine) complexes are inactive for catalytic olefin hydrogenation. Performing the reduction in the presence of internal alkynes such as diphenylacetylene and bis(trimethylsilyl)acetylene furnished the alkyne adducts [ArN=C(Me)C(Me)=NAr]Fe(η2-RC=CR) (R = Ph, SiMe3 ). Analogous olefin complexes with 1,5-cyclooctadiene and cycloctene have also been isolated using similar reduction procedures. The olefin adducts provide more active precatalysts than the alkyne compounds for the hydrogenation of 1-hexene. In each case, formation of rfarene adducts serves as a major catalyst deactivation pathway.
Synthesis, Reactivity, and Solid State Structures of Four-Coordinate Iron(II) and Manganese(II) Alkyl Complexes
Bart, Suzanne C.,Hawrelak, Eric J.,Schmisseur, Amanda K.,Lobkovsky, Emil,Chirik, Paul J.
, p. 237 - 246 (2008/10/09)
Synthesis and characterization of new, four-coordinate, high-spin iron(II) and manganese(II) complexes of the general form L2MR2 (L2 = neutral chelating ligand, R = alkyl) are described. Alkylation of the α-diimine complex, [ArN=C(Me)-C(Me)=NAr]FeCl2 (Ar = 2,6-diisopropylphenyl), as well as the enantiopure iron dichloride compounds, (-)-(sparteine)FeCl2 and (S)-(tBuBox)FeCl2 ((S)-(tBuBox) = 2,2-bis[2-[4(S)-(R′)-1,3-oxazolinyl]propane), with LiCH2SiMe3 afforded the corresponding dialkyl derivatives. Solution magnetic susceptibility measurements and X-ray diffraction studies reveal each of the new iron(II) bis-trimethylsilylmethyl complexes to be high-spin, S = 2, tetrahedral molecules. In addition (-)-(sparteine)Fe(CH2CMe3)2, (-)-(sparteine)Fe(CH2C6H5)2, and (S)-(tBuBox)Fe(CH2C6H5)2 were also prepared and characterized by NMR spectroscopy and elemental analysis. An enantiopure, high-spin, tetrahedral manganese(II) dialkyl complex, (-)-(sparteine)Mn(CH2SiMe3)2, has also been synthesized. The catalytic activity of the new iron complexes in carbon-carbon bond forming processes has been evaluated, and stoichiometric reactions of the dialkyls with olefins, carbon monoxide, and the Lewis acid B(C6F 5)3 have been examined.
