Volumc41, number 3

CHFMICAL PHYSICS LEITERS

August1976

EPR SPECTRA OF SEVEN COORDINATE IRON(IlI) COMPLEXES

S.A. COTTON
School of Chemical Scienqes, Utziversity of East Angiia, Nonvich NR4 7TJ, UK
Received 5 hfay 1976

EPR spectra are reported for two types of seven coordinate iron(II) complex. Spin-hamiltonian parameters are assigned;
it is possible to dtiinguish between six- and seven-coordinate species. The spectra of transferrn and conalbumin are discussed.

1. htroduction

3. Theory

Iron(III) is notable in exhibiting coordination numbers from 3 to 8 in its complexes [l] ; the possibility
of coordination number interconversion bas important
implkations in biological systems, as it can relate to
conformational changes in the protein.
Two well-defzed types of seven coordinate complex are provided by FeBXsY- (B = 2,13dimethyl3,6,9,12,18-pentaazabicyclo-12,3,1
octadeca-1(18),
2,12,14,16_pentane, X = NCS, Cl, Br, or 1; Y = ClO,

EPR spectra of highspin ds systems may be interpreted in terms of the spin-hamiltonian:

X=QWg-S+D(S;-$$)+E(S;

-S;)

and the ratio of E to D, X, is taken to fall in the range

0 - f , X = 0 implying axial symmetry [6]. Throughout this paper, g values are given as effective g values
k), defined by g = hvJ@H; the real g is taken to be isotropie and to have a value of 2.00.

or BF4) [2] and MFe(EDTA)OHL (M = ti, K, guandin-

ium; EDTA = ethylenediamnetetraacetetate) [3] . In

both bases the geometry of the coordination sphere is
a pentagonal bipyramid; in the former, fve nitrogen
atoms define the equatorial plane, whilst in the latter
the two nitrogen atoms and three oxygen atoms form
the (approximate) pentagon. On the other hand, iron
is six-coordinate in Fe(EDTAH)H20 [4] ; Williams et
al. have shown [5] that both six- and seven-coordinate
complexes of EDTA and hedta (hedta = hydroxyethylethylenediaminetriacetate) exist in solution, dependent
upon the solvent.

2. Experimental
The complexes were prepared by the literature
methods [2,3,5]. X-band EPR spectra were recorded
using a Varian E3 instrument; Q-band spectra of
(Fe, Ga) (EDTAH) HzO were got using a Varian
V4502 instrument at Imperial College, Londen.
6U6

4. Results ancl discussion

4.1. The complexes

FeBX$B&

The EPR spectra of the complexes FeBXlBFT fi

= NCS, Cl, Br, 1), obtained from nitromethane glasses
(fig. l), are characteristic of a system -withnear-axial
symmetry (X close to 0); X increases in the order Br, 1
< NCS < Cl. We estimate values of D and X to be ca.
0.5 cm-l and 0.03 (X = NCS) and ca. 0.3 cm-l and
0.13 (X = CI) respectively. Fcr X = Br and 1, the X
values are very close to zero and D values are in excess
of 1 cm-l . The fact that the largest value of X is associated wth the smallest value of D, and vice versa,
means that E, which reflects distortion in the plane of
the pentagon, is subject to less variation than D, as
would be expected.
The numerical sequence of D values, Cl C NCS
< Br, 1, can best be understood if the value of D in the

Volume 41, number 3

CHEMICAL PHYSICS L?ZlTERS

1 August 1976

9 105 GHz

Fig. 2. X-band EPR spectrum of Fe(hedta) (HzO)

gIycero1glass (votume ratio = 1: 1) at 77 K.

Fig. 1. X-band EPR spectra (77 K) of nitiomethane glassesof

FeBX$BF&X = NCS, Cl, 1); the bromide gvesvery simikx
spectra to the iodide.

thiocyanate complex has the opposite sign to that in

the other complexes, giving a sequence in accord with
expectations based on the spectrochemical
series. This
is in keeping with Mssbauer results, interpreted in
terms of a negative D value for the thiocyanate, and
positive values for the others [7]. A crystal-field pointcharge approach [8] would associate a negative D
vaiue with an elongation along the iron-halogen
axis,
as found [9] in Fe [N (Si(CH3)3}2] 3 ; this reversal of
the expected order parallels that found in iron(II1) &xphyrin systems, attributed to sr-bonding effects [S] ,
and suggests that the simple theory may not be of general applicablity.
IR glycerol-water
glasses, ah the FeBG complexes
give identical EPR spectra, virtually identical to Ahat of
FeB(NCS)z; we attribute this to tbe formation of
FeB(OH2)zi. The similarity of the spectra (hence D
and A) is in keeping with the fact that OH, and NCSare adjacent in the spectrochemical series [lol.
4.2. EDTA and hedta complexes
In contrast to the complexes considered in section
where the near-axiai symmetry manifest in the
EPR spectra is in keeping with the approximate Ds.,
structure, the complexes of EDTA and hedta exhibit

4.1,

in a water-

near-rhombic symmetry in their EPR spectra.

The X-band EPR spectrum of Fe(hedta)(HzO)z
in
water-glycerol
glasses contains three resonances in the
1000-2000 G regon (fig. 2); the intensity of the
sharpest resonance increases relative to the other two,
as the proportion of glycerol increases. This resonance
is characterised by the effective g values g; = 4.32 g
= 4.19; a similar situation is observed [l l] -in giycerol-water
glasses of Fe(EDTAH)(H20)
(g = 4.303
and 4.243) whilst we obtaing values of 4.31 and 4.24
from iron-doped In(EDTAH)@$O)
(see table 1).
From analysis of their absorption spectra, solutions
of the EDTA and hedta complexes in water and glycerol solutions are believed to involve-seven-coordinate
iron [S] ; thus we assign these sharp resonances to
seven-coordinate
Fe3+ ions with a large D value
(0.7 cm-1 [l 11) and a h value very close to $ .
in contrast, Fe(EDTAH)(HzO)
doped into the isostructural gallium analogue gves an EPR spectrum
showng a considerably greater splitting & = 4.59,4.23,
3.95 at 77 K); here we estimate D = 0.8 cm-, h
= 0.267. Here the iron is known to be six-coordinate
[4]. It certainly seems possible that iron may occupy
a six-coordinate site in Na Co(EDTA) -4H20 & = 4.64,
4.07,3.94; D = 0.769 cm-l , X = 0.307) [12,13].
In frazen dimethylsulphoxide
solutions of
a
single
broad
resonance
is observed
Fe(hedta)@&,
at g = 4.20; on adding water or glycerol, the same
three resonances appear which are seen in water-glycerol glasses. Iron is believed to be six-coordinate in the
dimethylsulphoxide
solutions [S] , so that the observed
SpeCbd
changes correspond to the transition from sixto sevencoordination.
607

Volume 41, number

Tab& 1
Efectiveg-values

1 August 1976

CHEMICAL PHYSICS LETTERS

CX-band; 77 K)

Probable
coordination
Fe&edta)Uia0)2
irr water-&cerol
Fe(EDTAIDH20
in water-glyc3Xol
Fe, In) (EDTAH)HtG
(Fe, Ga) (EDTAH)H20
Na(Fe, Co)(EDTA)4&0
Fe(hedta)(HzO)z
in DMSO

D Wm-z )

0.

0.33

4.32

4.19

4.19

0.7

0.327
0.267

4.243
4.24
4.23

4.243a)
4.24
3.95

0.8

4.303
4.31
4.59

0.769

0.307

4.64

4.07

3.94

number

4.20 Coroad)

5
6

a, Data from ref. [ll].

From the fact that we observe a multiplicity of

resonances for the seven coordinate hedta complex,
but not for the EDTA complex, it appears that a number of isomers are present involving different types of
solvation or, more probably different coordination by
the acid. We assign the sharp resonance observed for
both types of compound to a seven coordinate species
in which the iron atom is bound to two nitrogen
atoms and three carboxy-groups of the acid, and to
two oxygen atoms in solvent molecules.
Ihe combination of broad and sharp resonances
can give rise to an EPR spectrum with a close resemblance to the proteins condbumin and transferrin,
where, previously, the two iron-binding sites have been
said to be equivalent or nonequivalent
1141. Our data
show that it is possibie for a single complex to generate a similor spectrum by virtue of tbe ligand exhibiting varable polydentate behaviour, and susest that
this has important implications for the polyfunctiona]
groups often found in biologieal systems.

Acknowledgement

1 am most grateful to Dr. IC Garbett and Professor

R J.P. Williams for providing some samples of
(Ga, Fe)(EDTAH)(H20).

References
[l] S.A. Cotton, Coord. Chem. Rev. 8 (1972) 185.
[2] S.M. Nelson and D.H. Busch, Inorg. Chem. 8 (1969)
E.B.

and S. Hawkinson,

J. Am. Chem.

(1967)
720;
M.G.B. Drew, A.H. bin Othman, P.D.A. McIlroy
S.hl. Nelson, J. Chem_ Sec. Dalton (1975) 2507.

Sec.

1859;
89

and

[ 31 M.D. Lind, M.J. Hamor, T.A. Hamor and J.L. Hoard,

Inorg. Chem. 3 (1964) 34;

Ya.M. Nesterova, T.N. Polynova, L.I. Martynenko, and
N.I. Pechurova, J. Struct. Chem. 12 (1971) 1028.
[4 J C.H.L. KeMard, Inorg. Chim. Acts 1 (1967) 347.
(51 K. Garbett, G. Lang and R.J.P. Williams, J. Chem. Sec.
A

(1971) 3433.

i61 R.D.

Dowsing and J.F. Goson, J. Chem. Phys. 50 (1967)

294.
r71 F.A. Deeney and S.hf. Nelson, J. Phys. Chem. SoIids 34
(1973) 277.
181 hf. Gerloch, J. Lews and R.C. Slade, J. Chem. Sec. A
(1969) 1422.
P! D.C. Bradley, R.C. Copperthwaite, S.A. Cotton, J.F.
Gibson and K.D. Sales, J. Chem. Sec. Dalton (1973) 191.
[lol S.F.A. Kettle, Coordination compounds (Nclson, London,
1969).
1111 G. Lang, R. Aasa, K. Garbett and RJ.P. Williams, J.
Chem. Phys. 55 (1971) 4539.
1121 R Aast and T. Vanngard, Arkiv Kemi 24 (1965) 331.
[131 W.E. Blumber8, in: Ma8ntic resonance in biologica systems, eds. A. Ehrenbcrg, B.G. Malmstrom and T.
Varmgard (Pergamon, Londen, 1967).
r141 E.M. Price and J.F. Gbson, J. Biol. Chem. 247 (1972)
8031.

608

Fleischer