Fe_4 Cluster and a Buckled Macrocycle Complex from the Reduction of [(dmgBF_2)_(2)Fe(L)_2] (L = MeCN, ^(t)Bu^(i)NC)
Abstract
We report the syntheses, X-ray structures, and reductive electrochemistry of the Fe^(II) complexes [(dmgBF_2)_(2)Fe(MeCN)_2] (1; dmg = dimethylglyoxime, MeCN = acetonitrile) and [(dmgBF_2)Fe(^(t)Bu^(i)NC)_2] (2; ^(t)Bu^(i)NC = tert-butylisocyanide). The reaction of 1 with Na/Hg amalgam led to isolation and the X-ray structure of [(dmgBF_2)_(2)Fe(glyIm)] (3; glyIm = glyimine), wherein the (dmgBF_2)_2 macrocyclic frame is bent to accommodate the binding of a bidentate apical ligand. We also report the X-ray structure of a rare mixed-valence Fe4 cluster with supporting dmg-type ligands. In the structure of [(dmg_(2)BF_2)_(3)Fe_3(1/2dmg)_(3)Fe(O)_6] (4), the (dmgBF_(2))_2 macrocycle has been cleaved, eliminating BF_2 groups. Density functional theory calculations and electron paramagnetic resonance data are in accordance with a central FeIII ion surrounded by three formally Fe^(II)dmg_(2)BF_2 units.
Additional Information
© 2012 American Chemical Society. Received: October 19, 2011; Published: February 9, 2012. The authors thank Larry Henling and Michael Day for X-ray structures and Angelo Di Bilio for assistance with EPR spectra. We acknowledge Allen Oliver (University of Notre Dame) and Jeannette Krause (University of Cincinati) for X-ray data collection on 3 via the SCrALS program at Beamline 11.3.1, Advanced Light Source (LBNL), supported by the U.S. DOE, Energy Material Sciences Division. The Bruker KAPPA APEX II was purchased via an NSF CRIF:MU. The authors thank Nicole Fry for obtaining magnetic susceptibility data on 4. Funding sources: NSF Grant CHE-0802907 (to M.J.R., J.R.W., and H.B.G.); NSF Grant CHE-1042009 (to M.J.R.); Grant DOE-AC02-05CH11231 (synchrotron X-ray structure); NSF Grant CHE-0639094 (Mo Kα X-ray structures).Attached Files
Supplemental Material - ic202253v_si_001.pdf
Supplemental Material - ic202253v_si_002.cif
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Additional details
- Eprint ID
- 30235
- DOI
- 10.1021/ic202253v
- Resolver ID
- CaltechAUTHORS:20120420-132701817
- NSF
- CHE-0802907
- NSF Postdoctoral Fellowship
- CHE-1042009
- Department of Energy (DOE)
- DOE-AC02-05CH11231
- NSF
- CHE-0639094
- Created
-
2012-04-20Created from EPrint's datestamp field
- Updated
-
2021-11-09Created from EPrint's last_modified field
- Caltech groups
- CCI Solar Fuels