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44942-AC3
Characterization of Catalytic Imide Group Transfer Reactions with Iron Catalysts
Patrick L. Holland, University of Rochester
Narrative
Report (September 2008)
The report has
subsections corresponding to the three main goals of the proposal, and a fourth
section addresses unforeseen results gained under PRF support.
(1)
Characterization of Iron(III) Imido Complexes. The imido complex we have reported is shown at the left of Figure 1,
but it is too unstable for crystallography and is formed in less than 70%
yield. One of our aims is to create more stable imido intermediates for
crystallography and/or EXAFS analysis (Extended X-ray Absorption Fine
Structure, which shows metal-ligand bond distances). Figure 1 shows two ligand
modifications that we have made. First, adding tert-butyl groups to the
backbone of the ligand adds steric hindrance (Figure 1, center). Using this
ligand, we have generated solutions that contain 85-90% of the metastable imido
species, as judged by 1H NMR spectroscopy. We have obtained EXAFS
data (in collaboration with Serena DeBeer-George at Stanford Synchrotron
Laboratory), which show a 1.69 distance to a light-atom scatterer that has
50-70% occupancy. This short distance is indicative of the postulated Fe=N
double bond, and with the Fe=N distances in DFT computations by our
collaborator Thomas Cundari (University of North Texas). In fall 2008, a
student will travel to Germany to collect Mossbauer spectra of freshly prepared
samples, in collaboration with Eckhard Bill, Max-Planck-Institut, Mulheim,
Germany.
Another
ligand modification is shown at the right of Figure 1. This ligand has no weak
C-H bonds near the metal site, because the ortho-isopropyl groups are replaced by tert-butyl groups. In an exciting
development, an iron(I) complex of this ligand reacts with azide to form a
long-lived (days at room temperature) species with 1H NMR spectra
similar to the imido complexes of other ligands (which last only a few hours at
room temperature). These results are most consistent with formation of the
desired imido complex, and efforts to crystallize this complex for X-ray
diffraction analysis are underway.
(2)
Hydrogen Atom Abstraction and Amination Reactions. This section of the proposed work is dependent on
part (1), in that it requires a ligand that is not attacked by the imido group.
The promising preliminary results on the long-lived imido complex strongly suggest
that we will be able to address intramolecular H-atom abstractions soon.
(3)
Catalytic Carbodiimide and Aziridine Formation through Group Transfer. We are writing up our mechanistic studies on the
catalytic formation of tBuNCNAd from adamantyl azide (AdN3)
and t-butyl isocyanide (tBuNC), which was described in detail in the
2007 report. Interestingly, catalytic group transfer also occurs with CO to
form AdNCO, but the reaction with phosphines to give R3P=NAd does
not turn over. Attempts to observe aziridination have not yet been successful,
but ligand modifications (described above) are hoped to give promising results.
(4)
Other Results. Last year's report
described preliminary information on two interesting species: a tetrazene
complex LMeFe(AdNNNNAd), and a "hexazene" complex (LMeFe)2(AdNNNNNNAd).
Each of these contains a very interesting polynitrogen ligand, and each has
been evaluated in detail.
The
"hexazene" group (AdNNNNNNAd) is previously unknown in
transition-metal chemistry. We characterized the first two hexazene complexes,
and determined the oxidation state of the metal and ligand using Mossbauer
spectroscopy and magnetic susceptibility (in collaboration with Eckhard Bill). This
work was published as a Communication in J. Am. Chem. Soc., and was even covered as a Science Concentrate in Chemical
and Engineering News (April 28, 2008).
The
tetrazene complex LMeFe(AdNNNNAd) is interesting because it could be
formulated as an iron(I) complex with a neutral ligand, as an iron(II) complex
with a radical anion ligand, or an iron(III) complex with a dianionic ligand
(Figure 2). Mssbauer spectra and DFT calculations have definitively shown the
iron(II)-radical ligand resonance form is most accurate. Interestingly,
reduction by one electron gives [LMeFe(AdNNNNAd)]–,
in which the ligand, rather than the
metal, has been reduced. Although spectroscopic and theoretical studies are
ambiguous on the electron distribution in this compound, the crystal structure
shows clear signs of ligand reduction. This first detailed study on tetrazene
redox chemistry is also complete, and is being submitted to Angew.
Chem. for publication.
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