Inorganic Chemistry
Article
transmission mode at the BL17C wiggler beamline with a double-
crystal Si(111) monochromator. The energy resolution ΔE/E was
−4
estimated to be about 2 × 10 . High harmonics were rejected by Rh-
coated mirrors. The spectra were scanned from 6.912 to 8.006 keV. A
reference Fe foil is always measured simultaneously, in which the first
inflection point at 7112.0 eV of the Fe foil spectrum is used for energy
AUTHOR INFORMATION
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calibration. Ion chambers used to measure the incident (I ) and
0
transmitted (I) beam intensities were filled with a mixture of N and
2
Notes
He gases and a mixture of N and Ar gases, respectively.
2
The authors declare no competing financial interest.
The S K-edge data were collected in fluorescence mode at BL 16A
with a Si(111) monochromator. The energy resolution ΔE/E is 1.4 ×
ACKNOWLEDGMENTS
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1
0 . The energy is scanned from 2.42 to 2.77 keV. A Lytle detector
We gratefully acknowledge financial support from the National
Science Council of Taiwan. Authors thank Pei-Lin Chen and
Ting-Shen Kuo for single-crystal X-ray structural determina-
tions. We also thank NSRRC and NCHC for their support on
the hardware and software applied in this work.
was employed for fluorescence measurements in which the sample
chamber is filled with high-purity He gas to avoid air absorption.
Samples were ground to powder from single crystals and secured in
the bag made of 3.6 μm Mylar film. The absorption of the S K-edge
region of the empty bag made of 3.6 μm Mylar film was verified to be
negligible. The photon energy was calibrated to the maximum of the
2
5
first pre-edge feature of Na S O ·5H O at 2472.02 eV. The
2
2
3
2
REFERENCES
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uncertainty in preedge and edge energies is limited by the
(
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regions were performed on the ORCA package, version 2.8.0. The
coordinates used for geometry optimization of complexes [(NO) Fe-
2
t
t
(
μ-S Bu)] , rRRE-S Bu, 2, and 3 were based on the experimental
2
15b,16a
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structures taken from the X-ray diffraction experiments.
The
coordinate system employed is such that the origin is set as the center
between two Fe atoms; the x axis is collinear with the Fe1−Fe2
direction; the y axis is perpendicular to the x axis and in the direction
of the center to S1. The BP86 functional with the def2-TZVP(f) basis
set on the Fe, S, N, O, C, and H atoms was used in the geometry
(
1
Biochem. Pharmacol. 2002, 63, 485−493. (c) Frederik., A. C.; Wiegant,
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t
optimization. Complexes [(NO) Fe(μ-S Bu)] , 2, and 3 were
2
2
2
004, 104, 403−418. (e) Hayton, T. W.; Legzdins, P.; Sharp, W. B.
calculated at the closed-shell level because of its diamagnetism, but
t
Chem. Rev. 2002, 102, 935−991.
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rRRE-S Bu was done at the unrestricted open-shell level. The
(
2
optimized coordinates, bond lengths, bond angles, and corresponding
experimental crystal data of complexes 2 and 3 are listed in Tables S2
and S4 in the SI. These structures have been checked without
imaginary frequency in the ORCA package. The calculated stretching
frequencies of NO are also listed in Tables S3 and S5 in the SI. The
MO and TD-DFT calculation were done with the B3LYP exchange
̈
(
J. Biol. Chem. 1995, 270, 29244−29249. (d) Lee, M.; Arosio, P.; Cozzi,
A.; Chasteen, N. D. Biochemistry 1994, 33, 3679−3687. (e) Tsai, M.-
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Adams, M. W. W.; Cramer, S. P.; Lippard, S. J. J. Am. Chem. Soc. 2010,
̈
functional and def2-TZVP(f) basis set. The Lowdin population
analysis was used to obtain the contributions of Fe, S, and NO on each
MO. Isosurface plots of the MOs were generated using the Molekel
program, version 4.3, with an isovalue surface at 0.04 au.
1
(
32, 6914−6916.
Crystallography. Crystallographic data of complexes 1−3 were
4) Stadler, J.; Bergonia, H. A.; Di Silvio, M.; Sweetland, M. A.;
summarized in Tables S1−S3 in the SI, respectively. The crystals
3
Billiar, T. R.; Simmons, R. L.; Lancaster, J. R. Jr. Arch. Biochem.
Biophys. 1993, 302, 4−11.
chosen for X-ray diffraction studies measured 0.30 × 0.30 × 0.28 mm
3
for complex 1, 0.18 × 0.15 × 0.12 mm for complex 2, 0.35 × 0.23 ×
.06 mm for complex 3. Each crystal was mounted on a glass fiber and
3
(5) Cesareo, E.; Parker, L. J.; Pedersen, J. Z.; Nuccetelli, M.; Mazzetti,
A. P.; Pastore, A.; Federici, G.; Caccuri, A. M.; Ricci, G.; Adams, J. J.;
Parker, M. W.; Bello, M. L. J. Biol. Chem. 2005, 280, 42172−42180.
0
quickly coated in epoxy resin. Unit-cell parameters were obtained by
least-squares refinement. Diffraction measurements for complexes 1−3
were carried out on a SMART CCD (Nonius Kappa CCD)
diffractometer with graphite-monochromated Mo Kα radiation (λ =
(
6) (a) Cruz-Ramos, H.; Crack, J.; Wu, G.; Hughes, N. M.; Scott, C.;
Thomson, J. A.; Green, J.; Poole, K. R. EMBO J. 2002, 21, 3235−3244.
b) Kennedy, M. C.; Anthonline, E. W.; Beinert, H. J. Biol. Chem.
(
1
0.710 73 Å) and between 1.47 and 28.35° for complex 1, between 1.15
997, 272, 20340−20347. (c) Ding, H.; Demple, B. Proc. Natl. Acad.
and 26.41° for complex 2, and between 1.94 and 25.10° for complex 3.
Sci. U.S.A. 2000, 97, 5146−5150.
Least-squares refinement of the positional and anisotropic thermal
2
(7) (a) Tsai, M.-L.; Hsieh, C.-H.; Liaw, W.-F. Inorg. Chem. 2007, 46,
5110−5117. (b) Tsai, M.-L.; Liaw, W.-F. Inorg. Chem. 2006, 45, 6583−
6585.
parameters of all non-H atoms and fixed H atoms was based on F . A
27
SADABS absorption correction was made. The SHELXTL structure
28
refinement program was employed.
(
8) (a) Tsai, M.-L.; Chen, C.-C.; Hsu, I.-J.; Ke, S.-C.; Hsieh, C.-H.;
Chiang, K.-A.; Lee, G.-H.; Wang, Y.; Liaw, W.-F. Inorg. Chem. 2004,
43, 5159−5167. (b) Tsai, F.-T.; Chiou, S. J.; Tsai, M.-C.; Tsai, M.-L.;
Huang, H.-W.; Chiang, M.-H.; Liaw, W.-F. Inorg. Chem. 2005, 44,
ASSOCIATED CONTENT
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S
Supporting Information
X-ray crystallographic files in CIF format for structure
5
6
872−5881. (c) Tsai, M.-L.; Liaw, W.-F. Inorg. Chem. 2006, 45, 6583−
585. (d) Hung, M.-C.; Tsai, M.-C.; Lee, G.-H.; Liaw, W.-F. Inorg.
determinations of [PPN] [Fe(μ-OPh)(NO) ] , [PPN] [Fe(μ-
Chem. 2006, 45, 6041−6047. (e) Lu, T.-T.; Chiou, S.-J.; Chen, C.-Y.;
Liaw, W.-F. Inorg. Chem. 2006, 45, 8799−8806. (f) Chen, T.-N.; Lo,
2
2 2
2
t
S Bu)(NO) ] , and [K-18-crown-6 ether] [(NO) Fe(SEt) ],
2
2
2
2
2
4
086
dx.doi.org/10.1021/ic202332d | Inorg. Chem. 2012, 51, 4076−4087