E. Bill, P. Hildebrandt, K. Wieghardt et al.
FULL PAPER
1
.5 at the excitation wavelength, was deposited in a rotating cell. The
[1] J. Hockertz, S. Steenken, K. Wieghardt, P. Hildebrandt, J. Am. Chem.
Soc. 1993, 115, 11222.
Raman scattered light was detected in 908 with a scrambler placed in front
of the entrance slit of the spectrometer to account for the polarization
[2] A. Sokolowski, E. Bothe, E. Bill, T. Weyhermüller, K. Wieghardt,
Chem. Commun. 1996, 1671.
[3] B. Adam, E. Bill, E. Bothe, B. Goerdt, G. Haselhorst, K. Hildenbrand,
A. Sokolowski, S. Steenken, T. Weyhermüller, K. Wieghardt, Chem.
Eur. J. 1997, 3, 308.
�
1
sensitivity of the gratings. The spectral slit width was 2.8 cm . The spectra,
measured with an acquisition time of 50 s, were linearized in wavenumbers
�
1
yielding an increment between 0.1 and 0.25 cm and a total spectral range
�
1
of 500 cm . The contributions of the solvent and the supporting electrolyte
were subtracted.
[4] A. Sokolowski, J. Müller, T. Weyhermüller, R. Schnepf, P. Hilde-
brandt, K. Hildenbrand, E. Bothe, K. Wieghardt, J. Am. Chem. Soc.
Quantum chemical calculations: All quantum chemical computations were
performed by means of the Gaussian 92/DFT suite of ab initio programs
working under OpenVMS and were carried out on a DEC station 2000 as
described in detail elsewhere.[ For density functional theory (DFT)
computations we employed the Becke3LYP (B3LYP) combination of
1
997, 119, 8889.
[
[
[
5] A. Sokolowski, B. Adam, T. Weyhermüller, A. Kikuchi, K. Hilden-
brand, R. Schnepf, P. Hildebrandt, E. Bill, K. Wieghardt, Inorg. Chem.
8]
1
997, 36, 3702.
6] A. Sokolowski, H. Leutbecher, T. Weyhermüller, R. Schnepf, E.
Bothe, E. Bill, P. Hildebrandt, K. Wieghardt, J. Biol. Inorg. Chem.
[
43]
hybrid exchange and correlation functions.
For all neutral phenoxyl
radicals, the 6-31G* basis sets were applied.[ These basis sets are of
double zeta type for the valence electrons and they are augmented by
d-polarization functions for the carbon and oxygen atoms. For the
phenolate the 9s5p/4s2p basis set augmented with polarization functions
was employed. Moreover, for oxygen and carbon additional diffuse s- and
44]
1
997, 2, 444.
7] J. Müller, T. Weyhermüller, E. Bill, P. Hildebrandt, L. Ould-Moussa, T.
Glaser, K. Wieghardt, Angew. Chem. 1998, 110, 637; Angew. Chem.
Int. Ed. 1998, 37, 616.
[
[
8] R. Schnepf, A. Sokolowski, J. Müller, V. Bachler, K. Wieghardt, P.
Hildebrandt, J. Am. Chem. Soc. 1998, 120, 2352.
[
45]
p-functions are provided with exponents of 0.059 and 0.034, respectively.
The frequencies were scaled by a factor of 0.9744 as discussed previously.
[
8]
9] a) M. M. Whittaker, J. W. Whittaker, J. Biol. Chem. 1988, 263, 6074;
b) M. M. Whittaker, V. D. DeVito, S. A. Asher, J. W. Whittaker, J.
Biol. Chem. 1989, 264, 7104; c) M. L. McGlashen, D. D. Eads, T. G.
Spiro, J. W. Whittaker, J. Phys. Chem. 1995, 99, 4918; d) K. Clark, J. E.
Penner-Hahn, M. M. Whittaker, J. W. Whittaker, J. Am. Chem. Soc.
1990, 112, 6433.
X-ray crystallography: A suitable single crystal (0.45 Â 0.11 Â 0.11 mm) of
III dimet
[
Fe
L
3
] ´ 2CH CN was mounted on a glass fiber on a Siemens SMART
diffractometer. Measurements were performed with graphite-monochro-
mated MoKa radiation (l 0.71073 ). Intensities were corrected for
absorption effects with the SADABS program (G. M. Sheldrick, 1994). The
structure was solved by direct methods with SHELXTL. Non-hydrogen
atoms were refined with anisotropic thermal parameters; hydrogen atoms
were included with isotropic thermal parameters. One acetonitrile solvent
molecule was disordered. The disorder was satisfactorily modeled by two
positions with occupancy factors of 0.5 for two terminal atoms treated as
carbon (C(41), C(41X)). Crystallographic data are given in Table 7.
[10] M. M. Whittaker, P. J. Kersten, N. Nakamura, J. Sanders-Loehr, E. S.
Schweizer, J. W. Whittaker, J. Biol. Chem. 1996, 271, 681.
[11] a) U. Auerbach, U. Eckert, K. Wieghardt, B. Nuber, J. Weiss, Inorg.
Chem. 1990, 29, 938; b) U. Auerbach, T. Weyhermüller, K. Wieghardt,
B. Nuber, E. Bill, C. Butzlaff, A. X. Trautwein, Inorg. Chem. 1993, 32,
508.
[
12] P. G. Debrunner in Mössbauer Spectroscopy of Iron Porphyrins,
Vol. III (Ed.: P. G. Debrunner), VCH, Weinheim, 1989, pp. 137 ± 234.
13] U. Russo, G. J. Long, in Mössbauer Spectroscopic Studies of the High
Oxidation States of Iron, Vol. 3 (Eds.: U. Russo, G. J. Long), Plenum,
New York, London, 1989, pp. 289 ± 329.
Table 7. Crystallographic data for [FeIIILdimet] ´ 2MeCN.
[
chem formula
fw
space group
a []
b []
c []
37 5 9
C H48FeN O
762.65
P2 /n
[14] D. Mandon, R. Weiss, K. Jayaraj, A. Gold, J. Terner, E. Bill, A. X.
Trautwein, Inorg. Chem. 1992, 31, 4404 ± 4409.
[15] L. Shu, J. C. Nesheim, K. Kauffmann, E. Münck, J. D. Lipscomb, L.
Que, Science 1997, 275, 515.
[16] T. Jüstel, T. Weyhermüller, K. Wieghardt, E. Bill, M. Lengen, A. X.
Trautwein, P. Hildebrandt, Angew. Chem. 1995, 107, 744; Angew.
Chem. Int. Ed. Engl. 1995, 34, 669.
1
12.373(2)
26.448(5)
12.398(2)
116.00(2)
3646.5(11)
4
b [8]
V [ ]
3
Z
T [K]
1
100(2)
1.389
4.76
[17] T. Jüstel, M. Müller, T. Weyhermüller, C. Kressl, E. Bill, P.
Hildebrandt, M. Lengen, M. Grodzicki, A. X. Trautwein, B. Nuber,
K. Wieghardt, Chem. Eur. J. 1999, 5, 793 ± 810.
calcd [g cm 3]
�
�
1
m(MoKa) [cm
]
refl. collected
unique refl./[I > 2s(I)]
no. parameters
31587
7604 / 5518
477
[18] U. Knof, T. Weyhermüller, K. Wieghardt, E. Bill, C. Butzlaff, A. X.
Trautwein, Angew. Chem. 1993, 105, 1701; Angew. Chem. Int. Ed.
Engl. 1993, 32, 1635.
2
q
max [8]
55.0
0.0642
0.1296
[19] K. L. Kostka, B. G. Fox, M. P. Hendrich, T. J. Collins, C. E. F. Rickard,
L. J. Wright, E. Münck, J. Am. Chem. Soc. 1993, 115, 6746.
[20] T. J. Collins, K. L. Kosta, E. Münck, E. S. Uffelmann, J. Am. Chem.
Soc. 1990, 112, 5637.
[
a]
R1 [I > 2q(I)]
wR2 [I > 2q(I)]
[
b]
2
2
)2]/S[w(F 2)2]1/2,
[
a] R1SjjF
o
2
j � jF
c
jj/SjF
o
j.
[b] wR2[S[w(F
o
� F
c
o
[
[
[
[
21] T. J. Collins, B. G. Fox, Z. G. Hu, K. L. Kosta, E. Münck, C. E. F.
Rickard, L. J. Wright, J. Am. Chem. Soc. 1992, 114, 8724.
22] D. Sellmann, S. Emig, F. W. Heinemann, Angew. Chem. 1997, 109,
2
2
2
2
where w1/s (F
o
)(aP) bP, P(F
o
2F
c
)/3.
1
808; Angew. Chem. Int. Ed. Engl. 1997, 36, 1734.
23] D. Sellmann, S. Emig, F. W. Heinemann, F. Knoch, Angew. Chem.
997, 109, 1250; Angew. Chem. Int. Ed. Engl. 1997, 36, 1201.
Crystallographic data (excluding structure factors) have been deposited
with the Cambridge Crystallographic Data Centre as supplementary
publication no. CCDC-102115. Copies of the data can be obtained free of
charge on application to CCDC, 12 Union Road, Cambridge CB21EZ, UK
1
24] P. Gütlich, R. Link, A. Trautwein, Mössbauer Spectroscopy and
Transition Metal Chemistry, Springer, Berlin, Heidelberg, New York,
(
fax: (44)1223-336-033; e-mail: deposit@ccdc.cam.ac.uk).
1
978.
[25] E. Münck, in Iron-Sulfur Proteins, Vol. 3 (Ed.: T. G. Spiro), Wiley,
New York, 1982, p. 147.
[
26] For the concentrated solution (1.5mm) the spectra showed an
additional broad absorption-derivative signal at g ꢁ 2 that changed
upon dilution. However, the pattern persisted even at 20mm concen-
tration and varied for different preparations. We suppose that the
neutral complexes tend to aggregate in solution. The resulting
enhanced intermolecular spin-spin interaction could give rise to the
Acknowledgments
The authors thank the Fond der Chemischen Industrie for financial
support. P.H. acknowledges a Heisenberg fellowship from the Deutsche
Forschungsgemeinschaft.
2
564
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