416 Abstracts

H57 M O S S B A U E R STUDIES OF A NOVEL N O N - H E M E

I N T E R M E D I A T E SPIN IRON(lID E X C H A N G E - C O U P L E D
T O A LIGAND RADICAL
Karl E. Kauffmann," Michael Bartos," Christopher Kldweil," Scott W. Gordon-
Wylie," Terrenee J. Collins," George C. Clark, b Susan T. Weintraub," and Eckard
Mfinek"
°Department of Chemistry, Carnegie Mellon University, Pittsburgh, PA 15213, USA;
bDepartment of Chemistry, University of Aucklana~ Private Bag 920119, Auckland, New
Zealand; c Department of Pathology, University of Texas Health Science Center at San
Antonio, San Antonio, TX 78284, USA.

The structure and magnetic behavior of [Ph4P][Fe(III) DMOB

(H20)], 1, is described. The M6ssbauer spectra of 1 have 5 = 0.14(2) mm/s
and AEo = 4.28(4) mm/s. EPR studies of 1 dissolved in HeO reveal an S =
3/2 system with resonances at g = 4.5 and 3.3. High-field M6ssbauer spectra
can be fit well assuming an S = 3/2 spin Hamiltonian.
Upon a 1-electron oxidation of 1, complex 2 is obtained.
Crystallographic analysis of 2 shows that the iron is five-coordinate with one
H20 ligand coordinated in the axial position.
iI~,o.__!i

c.,o /
CHrOmo
FIGUREL Stradure of (2).
M6ssbaner spectra of 3 have 6 = 0.14(1) mm/s and AEo = 3.97(2) mm/s.
Surprisingly, 1 and 2 have the same isomeric shifts. Since 6 is sensitive to
the oxidation state of iron, this observation suggests that the oxidation is
lignnd-centered rather than metal-based. Moreover, the M6ssbauer data
reveal that 2 behaves as an integer-spin complex. Magnetization data on 2
taken from 2 - 300 K show that ~ n saturates to -3.0 ttB, which is close to
the ~eF = 2.83 ttB expected for a spin-only S = 1 system. The MOssbauer
spectra can be fit well to a S = 1 spin Hamiltonlan. These observations
suggest that the magnetic behavior of 2 should be described with a
Hamiltonian that considers antiferromagnetic coupling between an S = 3/2
Fe TM site and a ligand-based radical. We found that the data are described
well f o r J • 200 c~n-I (H = JSI~S2). Ligand-based oxidation is also indicated
by the structural parameters of the aromatic moiety.