Diiron Azadithiolates as Models for the Active Site of Fe-Only Hydrogenases
FULL PAPER
methods using the SHELXS-97[25] program and refined by full-
matrix least-squares techniques (SHELXL-97[26]) on F2. Hydrogen
atoms were located by using the geometric method. Details of crys-
tal data, data collections, and structure refinements are summa-
rized in Table 4. CCDC-293719 (2) and -293720 (3) contain the
supplementary crystallographic data for this paper. These data can
be obtained free of charge from The Cambridge Crystallographic
Data Centre via www.ccdc.cam.ac.uk/data_request/cif.
100, 3683–3688; c) D. J. Evans, C. J. Pickett, Chem. Soc. Rev.
2003, 32, 268–275; d) X. Liu, S. K. Ibrahim, C. Tard, C. J. Pick-
ett, Coord. Chem. Rev. 2005, 249, 1641–1652.
[2] a) M. Frey, ChemBioChem 2002, 3, 153–160; b) S. P. J. Al-
bracht, Biochem. Acta 1994, 1188, 167–204; c) A. Volbeda,
M. H. Charon, C. Piras, E. C. Hatchikian, M. Frey, J. C. Fonte-
cilla-Camps, Nature 1995, 373, 580–587; d) R. Cammack, Na-
ture 1999, 397, 214–215; e) M. W. W. Adams, E. I. Stiefel, Sci-
ence 1998, 282, 1842–1843; f) J. Alper, Science 2003, 299, 1686–
1687.
Table 4. Crystal data and structural refinement details for 2 and 3.
[3] M. W. W. Adams, Biochim. Biophys. Acta 1990, 1020, 115–145.
[4]
a) J. W. Peters, W. N. Lanzilotta, B. J. Lemon, L. C. Seefeldt,
Science 1998, 282, 1853–1858; b) Y. Nicolet, C. Piras, P. Leg-
rand, C. E. Hatchikian, J. C. Fontecilla-Camps, Struct. (Lon-
don) 1999, 7, 13–23.
a) Y. Nicolet, B. J. Lemon, J. C. Fontecilla-Caps, J. W. Peters,
Trends Biochem. Sci. 2000, 25, 138–143; b) Y. Nicolet, A. L.
Lacey, X. Vernede, V. M. Fernandez, E. C. Hatchikian, J. C.
Fontecilla-Camps, J. Am. Chem. Soc. 2001, 123, 1596–1601.
H. Fan, M. B. Hall, J. Am. Chem. Soc. 2001, 123, 3828–3829.
a) J. D. Lawrence, H. Li, T. B. Rauchfuss, M. Bénard, M.-M.
Rohmer, Angew. Chem. Int. Ed. 2001, 40, 1768–1771; b) H. Li,
T. B. Rauchfuss, J. Am. Chem. Soc. 2002, 124, 726–727; c) S.
Ott, M. Kritikos, B. Åkermark, L. Sun, Angew. Chem. Int. Ed.
2003, 42, 3285–3288.
a) X. Zhao, I. P. Georgakaki, M. L. Miller, J. C. Yarbrough,
M. Y. Darensbourg, J. Am. Chem. Soc. 2001, 123, 9710–9711;
b) F. Gloaguen, J. D. Lawrence, M. Schmidt, S. R. Wilson,
T. B. Rauchfuss, J. Am. Chem. Soc. 2001, 123, 12518–12527; c)
E. J. Lyon, I. P. Georgakaki, J. H. Reibenspies, M. Y. Dar-
ensbourg, J. Am. Chem. Soc. 2001, 123, 3268–3278; d) M. Ra-
zavet, S. C. Davies, D. L. Hughes, J. E. Barclay, D. J. Evans,
S. A. Fairhurst, X. Liu, C. J. Pickett, Dalton Trans. 2003, 586–
595.
a) X. Zhao, I. P. Georgakaki, M. L. Miller, R. Mejia-Rodrig-
uez, C.-Y. Chiang, M. Y. Darensbourg, Inorg. Chem. 2002, 41,
3917–3928; b) J. L. Nehring, D. M. Heinekey, Inorg. Chem.
2003, 42, 4288–4292.
2
3
Empirical formula
Mr [g·mol–1
C15H11Fe2NO7S2 C32H26Fe2NO6PS2
493.07
]
727.33
triclinic
P1
Crystal system
Space group
a [Å]
b [Å]
c [Å]
orthorhombic
Pca2(1)
15.995(4)
9.306(3)
24.928(8)
90
[5]
¯
9.691(8)
10.371(8)
17.578(16)
72.857(12)
78.003(18)
87.556(13)
1651(2)
2
1.463
744
1.097
50.02
8267
5706
–11 Յ h Յ 9
–12 Յ k Յ 12
–16 Յ l Յ 20
0.0806
0.1324
1.019
0.731/–0.519
[6]
[7]
α [°]
β [°]
90
90
γ [°]
V [Å3]
Z
3710.7(19)
8
1.765
1984
1.826
52.98
20521
6006
–20 Յ h Յ 1 9
–11 Յ k Յ 9
–22 Յ l Յ 31
0.0463
0.0921
1.058
ρcalcd. [g·cm–3
F(000)
]
[8]
µ [mm–1
]
2θmax [°]
Reflections collected
Independent reflections
Index ranges
R
Rw
[9]
Goodness-of-fit
Largest diff peak/hole [e·Å–3
]
1.136/–0.448
[10]
[11]
F. Gloaguen, J. D. Lawrence, T. B. Rauchfuss, J. Am. Chem.
Soc. 2001, 123, 9476–9477.
D. Chong, I. P. Georgakaki, R. Mejia-Rodriguez, J. Sanabria-
Chinchilla, M. P. Soriaga, M. Y. Darensbourg, Dalton Trans.
2003, 4158–4163.
S. Ott, M. Kritikos, B. Åkermark, L. Sun, R. Lomoth, Angew.
Chem. Int. Ed. 2004, 43, 1006–1009.
J. D. Lawrence, H. Li, T. B. Rauchfuss, Chem. Commun. 2001,
1482–1483.
L.-C. Song, Acc. Chem. Res. 2005, 38, 21–28.
D. Seyferth, R. S. Henderson, L.-C. Song, Organometallics
1982, 1, 125–133.
J. P. Collman, L. S. Hegedus, J. R. Norton, R. G. Finke, Prin-
ciples and Applications of Organotransition Metal Chemistry,
2nd ed., University Science Books, Mill Valley, CA, 1987.
E. J. Lyon, I. P. Georgakaki, J. H. Reibenspies, M. Y. Dar-
ensbourg, Angew. Chem. Int. Ed. 1999, 38, 3178–3180.
L.-C. Song, Z.-Y. Yang, H.-Z. Bian, Y. Liu, H.-T. Wang, X.-F.
Liu, Q.-M. Hu, Organometallics 2005, 24, 6126–6135.
I. Bhugun, D. Lexa, J.-M. Saveant, J. Am. Chem. Soc. 1996,
118, 3982–3983.
Electrochemistry: Acetonitrile (Fisher Chemicals, HPLC grade) was
the solvent used for the electrochemistry. A solution of 0.1
nBu4NPF6 in MeCN was used as the electrolyte in all of the cyclic
voltammetric experiments. The electrolyte solution was degassed
by bubbling N2 through it for 10 min before measurements were
taken. Electrochemical measurements were made using a BAS Ep-
silon potentiostat. All voltammograms were obtained in a three-
electrode cell with a 3-mm-diameter glassy carbon working elec-
trode, a platinum counter electrode and an Ag/Ag+ (0.01 AgNO3/
0.1 nBu4NPF6 in MeCN) reference electrode under N2 or CO.
The working electrode was polished with 0.05 µm alumina paste
and sonicated in water for 10 min. Bulk electrolysis was run on a
vitreous carbon rod (ca. 3 cm2) in a two-compartment, gas tight,
H-type electrolysis cell containing ca. 18 mL of MeCN. All poten-
tials are quoted against the ferrocene/ferrocenium (Fc/Fc+) poten-
tial.
[12]
[13]
[14]
[15]
[16]
[17]
[18]
[19]
[20]
[21]
Acknowledgments
T. Liu, M. Wang, Z. Shi, H. Cui, W. Dong, J. Chen, B. Åkerm-
ark, L. Sun, Chem. Eur. J. 2004, 10, 4474–4479.
R. Mejia-Rodriguez, D. Chong, J. H. Reibenspies, M. P. Sori-
aga, M. Y. Darensbourg, J. Am. Chem. Soc. 2004, 126, 12004–
12014.
We are grateful to the National Natural Science Foundation of
China and the Specialized Research Fund for the Doctoral Pro-
gram of Higher Education of China for financial support of this
work.
1
[22]
The H NMR (CD3CN) data of 2 in HOAc are: δ = 7.02, 6.99,
6.91, 6.89 (AB q, 4 H, C6H4), 4.49 (s, 4 H, 2 CH2), 3.85 (s, 3
H, CH ) ppm. The IR (CH CN) data are: ν = 2074 (s), 2037
˜
3
3
1
[1] a) M. Y. Darensbourg, E. J. Lyon, J. J. Smee, Coord. Chem. Rev.
2000, 206–207, 533–561; b) M. Y. Darensbourg, E. J. Lyon, X.
Zhao, I. P. Georgakaki, Proc. Natl. Acad. Sci. U. S. A. 2003,
(vs), 1995 (vs) (CϵO) cm–1. The H NMR (CD3CN) data of 2
without HOAc are: δ = 7.02, 6.99, 6.91, 6.89 (AB q, 4 H,
C6H4), 4.49 (s, 4 H, 2 CH2), 3.85 (s, 3 H, CH3) ppm. The IR
Eur. J. Inorg. Chem. 2006, 3204–3210
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