799270-33-0Relevant academic research and scientific papers
Synthesis and hydrogenation of bis(imino)pyridine iron imides
Bart, Suzanne C.,Lobkovsky, Emil,Bill, Eckhard,Chirik, Paul J.
, p. 5302 - 5303 (2007/10/03)
Treatment of the iron bis(dinitrogen) complex, (iPrPDI)Fe(N2)2 (iPrPDI = (2,6-iPr2C6H3N=CMe)2C5H3N), with a series of aryl azides resulted in loss of 3 equiv of N2 and formation of the corresponding four-coordinate iron imide compounds, (iPrPDI)Fe(NAr). These complexes, two of which (Ar = 2,6-iPr2-C6H3 and 2,4,6-Me3-C6H2) have been characterized by X-ray diffraction, are significantly distorted from planarity. The metrical parameters in combination with Moessbauer spectroscopic and SQUID magnetic data suggest an intermediate spin iron(III) center antiferromagnetically coupled to a ligand-centered radical. Nitrene group transfer has been accomplished by addition of 1 atm of CO, yielding aryl isocyanates, ArNCO, and (iPrPDI)Fe(CO)2. Hydrogenation of the more sterically hindered members of the series furnished free aniline and the previously reported iron dihydrogen complex. Catalytic aryl azide hydrogenation has also been achieved, and the observed relative rates are consistent with N-H bond formation as the rate-determining step in aniline formation. Copyright
Preparation and molecular and electronic structures of iron(0) dinitrogen and silane complexes and their application to catalytic hydrogenation and hydrosilation
Bart, Suzanne C.,Lobkovsky, Emil,Chirik, Paul J.
, p. 13794 - 13807 (2007/10/03)
Reduction of the five-coordinate iron(II) dihalide complexes ( iPrPDI)FeX2 (iPrPDI = ((2,6-CHMe 2)2C6H3N=CMe)2C 5H3N; X = Cl, Br) with sodium amalgam under 1 atm of dinitrogen afforded the square pyramidal, high spin iron(0) bis(dinitrogen) complex (iPrPDI)Fe(N2)2. In solution, ( iPrPDI)Fe(N2)2 loses 1 equiv of N2 to afford the mono(dinitrogen) adduct (iPrPDI)Fe(N2) 2. Both dinitrogen compounds serve as effective precatalysts for the hydrogenation and hydrosilation of olefins and alkynes. Effecient catalytic reactions are observed with low catalyst loadings (≤0.3 mol %) at ambient temperature in nonpolar media. The catalytic hydrosilations are selective in forming the anti-Markovnikov product. Structural characterization of a high spin iron(0) alkyne and a bis(silane) σ-complex has also been accomplished and in combination with isotopic labeling studies provides insight into the mechanism of both catalytic C-H and catalytic C-Si bond formation.
