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Fe_4 Cluster and a Buckled Macrocycle Complex from the Reduction of [(dmgBF_2)_(2)Fe(L)_2] (L = MeCN, ^(t)Bu^(i)NC)

Rose, Michael J. and Winkler, Jay R. and Gray, Harry B. (2012) Fe_4 Cluster and a Buckled Macrocycle Complex from the Reduction of [(dmgBF_2)_(2)Fe(L)_2] (L = MeCN, ^(t)Bu^(i)NC). Inorganic Chemistry, 51 (4). pp. 1980-1982. ISSN 0020-1669. doi:10.1021/ic202253v.

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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.

Item Type:Article
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Winkler, Jay R.0000-0002-4453-9716
Gray, Harry B.0000-0002-7937-7876
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).
Group:CCI Solar Fuels
Funding AgencyGrant Number
NSF Postdoctoral FellowshipCHE-1042009
Department of Energy (DOE)DOE-AC02-05CH11231
Issue or Number:4
Record Number:CaltechAUTHORS:20120420-132701817
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Official Citation:Fe4 Cluster and a Buckled Macrocycle Complex from the Reduction of [(dmgBF2)2Fe(L)2] (L = MeCN, tBuiNC) Michael J. Rose, Jay R. Winkler, and Harry B. Gray Inorganic Chemistry 2012 51 (4), 1980-1982
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:30235
Deposited By: Jason Perez
Deposited On:20 Apr 2012 21:31
Last Modified:09 Nov 2021 19:43

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