Journal of the American Chemical Society
Article
(7) See for example: (a) Telser, J.; Drago, R. S. Inorg. Chem. 1984,
23, 3114. (b) Cukiernik, F. D.; Luneau, D.; Marchon, J.-C.; Maldavi, P.
Inorg. Chem. 1998, 37, 3698. (c) Jimenez-Aparicio, R.; Urbanos, F. A.;
́
Arrieta, J. M. Inorg. Chem. 2001, 40, 613. (d) Handa, M.; Sayama, Y.;
Mikuriya, M.; Nukuda, R.; Hiromitsu, I.; Kasuga, K. Bull. Chem. Soc.
Jpn. 1995, 68, 1647. (e) Cheng, W.-Z.; Cotton, F. A.; Dalal, N. S.;
Murillo, C. A.; Ramsey, C. M.; Ren, T.; Wang, X. J. Am. Chem. Soc.
2005, 127, 12691. (f) Liao, Y.; Shum, W. W.; Miller, J. S. J. Am. Chem.
(13) For reference, the closest approach of a fluorine atom to a
ruthenium atom is over 4.7 Å. The Ru(1)···F(3A) separation is
4.74(1), 4.75(1), and 5.04(2) Å at 200, 298, and 27 K, respectively.
(14) To our knowledge there is only one structure of a compound
5+
with an Ru2 core that is devoid of an axial ligand (Ru2(DPhF)3Br2),
but this is not a paddlewheel species. This compound has a dimetal
core spanned by the bridging formamidinate bridges. The remaining
equatorial positions are occupied by the two halide species. The Ru−
Ru distance is 2.4011(4) Å and its magnetism is intermediate between
that that is expected from either species with three or one unpaired
Soc. 2002, 124, 9336. (g) Barral, M. C.; Herrero, S.; Jimen
R.; Torres, M. R.; Urbanos, F. A. Angew. Chem., Int. Ed. 2005, 44, 305.
(h) Barral, M. C.; Gallo, T.; Herrero, S.; Jimenez-Aparicio, R.; Torres,
́
ez-Aparicio,
electron. See: Barral, M. C.; Gallo, T.; Herrero, S.; Jimen
R.; Torres, M. R.; Urbanos, F. A. Chem.Eur. J. 2007, 13, 10088.
(15) Barral, M. C.; Gonzalez-Prieto, R.; Jimenez-Aparicio, R.; Priego,
́
ez-Aparicio,
́
M. R.; Urbanos, F. A. Chem.Eur. J. 2007, 13, 10088. (i) Miyasaka,
H.; Motokawa, N.; Matsunaga, S.; Yamashita, M.; Sugimoto, K.; Mori,
T.; Toyota, N.; Dunbar, K. J. Am. Chem. Soc. 2010, 132, 1532.
́
́
J. L.; Torres, M. R.; Urbanos, F. A. Eur. J. Inorg. Chem. 2003, 2339 and
the references therein.
(j) Barral, M. C.; Gonzal
R.; Priego, J. L.; Royer, E. C.; Torres, M. R.; Urbanos, F. A. Polyhedron
2004, 23, 2637. (k) Delgado, P.; Gonzalez-Prieto, R.; Jimenez-
Aparicio, R.; Perles, J.; Priego, J.; Torress, R. M. Dalton Trans. 2012,
41, 11866. (l) Delgado-Martínez, P.; Gonzalez-Prieto, R.; Gomez-
García, C. J.; Jimenez-Aparicio, R.; Priego, J. L.; Torres, M. R. Dalton
́ ́
ez-Prieto, R.; Herrero, S.; Jimenez-Aparicio,
(16) The magnetic data for 2, which is similar to that of diruthenium
tetracarboxylates, show a highly anisotropic behavior with a strong
ZFS, which can be modeled using the following set of equations:
́
́
́
1 + 9 exp −2D
́
Ng 2β2
kT
(
)
kT
χ =
Trans. 2014, 43, 3227. (m) Haque, F.; del Barco, E.; Fishman, R. S.;
Miller, J. S. Polyhedron 2013, 64, 73. (n) Da Silva, J. G.; Miller, J. S.
Inorg. Chem. 2013, 52, 1418. (o) Her, J.-H.; Stephens, P. W.; Kennon,
B. S.; Liu, C.; Miller, J. S. Inorg. Chim. Acta 2010, 364, 172. (p) Ikeue,
T.; Kimura, Y.; Karino, K.; Iida, M.; Yamahi, T.; Hiromitsu, I.;
Sugimori, T.; Yoshioka, D.; Mikuriya, M.; Handa, M. Inorg. Chem.
Commun. 2013, 33, 133.
2D
⎡
⎤
4 1 + exp −
(
)
⎦
⎣
kT
3kT
D
2D
kT
⎡
⎤
⎦
2
Ng⊥ β2
4 +
1 − exp −
(
)
(
)
⎣
χ =
⊥
2D
⎡
⎤
kT
4 1 + exp −
(
)
⎦
⎣
kT
(8) For an account of electronic configurations in paddlewheel
compounds, see: Falvello, L. R.; Foxman, B. M.; Murillo, C. A. Inorg.
Chem. 2014, 53, in press. dx.doi.org/10.1021/ic500119h.
where χ = (χ∥ + 2χ⊥)/3, N is Avogadro’s number, D is the ZFS
parameter in cm−1, β is the Bohr magneton, k is the Boltzmann
constant, and T is the temperature in Kelvin. The modeling of the data
of 2 with these equations yields anisotropic values of g∥ and g⊥ of
1.72(4) and 2.02(1), respectively, which are consistent with the EPR
data (vide supra), and the value of D of 75(3) is consistent to that of
similar diruthenium complexes.
(9) The chemical composition of this system is [Ru2(OAc)-
(DPhF)3(H2O)](SO3CF3)·THF. In both paddlewheel molecules
there is an axial water molecule that is hydrogen-bonded to a triflate
anion, but in only one of the Ru25+ species there is a hydrogen-bonded
interaction between water and the THF molecule. For the latter, the
Ru−Ru distances are 2.3637(6) Å at 30 K and 2.3255(5) Å at 298 K,
and for the molecule that is devoid of hydrogen bonded interactions to
the THF molecule these distances are 2.2950(6) Å and 2.3064(5) Å,
(17) The crystal structure of 1 has interstitial CH2Cl2 with an
occupancy of 0.5, which plays no role in its structure since it resides in
a noncoordinating position away from the axial location.
(18) Kondo, M.; Hamatami, M.; Kitagawa, S. J. Am. Chem. Soc. 1998,
120, 455.
respectively. See: Cotton, F. A.; Herrero, S.; Jimen
Murillo, C. A.; Urbanos, F. A.; Villagran, D.; Wang, X. J. Am. Chem.
Soc. 2007, 129, 12666.
́
ez-Aparicio, R.;
́
(19) For large values of D and S = 3/2, the effective (ge) and actual g-
values are related by g⊥ = g⊥e /2 and g∥ = ge∥. See ref 7e or Pilbrow, J. R.
J. Mag. Res. 1978, 31, 479. In addition, giso = (2g⊥ + g∥)/3.
(20) Multiple Bonds between Metal Atoms; Cotton, F. A., Murillo, C.
A., Walton, R. A., Eds.; Springer Science and Business Media, Inc.:
New York, 2005.
(10) For references on noncoordinating anions, see, for example:
(a) Krossing, I.; Raabe, I. Angew. Chem., Int. Ed. 2004, 43, 2066 and
the references therein. (b) Rach, S. F.; Kuhn, F. E. Chem. Rev. 2009,
̈
109, 2061. (c) Adams, H.; Fenton, D. E.; McHugh, P. E.; Potter, T.
Inorg. Chim. Acta 2002, 331, 117. (d) Sharma, R. P.; Singh, A.;
Venugopalan, P.; Harrison, W. T. A. J. Mol. Struct. 2011, 994, 6.
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Chem. Soc. 2000, 122, 416.
(22) Cotton, F. A.; Hillard, E. A.; Liu, C. Y.; Murillo, C. A.; Wang,
W.; Wang, X. Inorg. Chim. Acta 2002, 337, 233.
(23) Cotton, F. A.; Hillard, E. A.; Murillo, C. A. J. Am. Chem. Soc.
2002, 124, 5658.
(11) The use of a noncoordinating solvent is essential. Many
5+
compounds having Ru2 cores with BF4 or other noncoordinating
counterions are known, but without exception they contain axial
ligands such as H2O, acetonitrile, and other coordinating neutral
species. For examples, see: (a) Bino, A.; Cotton, F. A.; Felthouse, T. R.
Inorg. Chem. 1979, 18, 2599. (b) Cotton, F. A.; Lu, J.; Yokochi, A.
Inorg. Chim. Acta 1998, 275−276, 447. (c) Anez, E.; Herrero, S.;
(24) Cotton, F. A.; Daniels, L. M.; Murillo, C. A.; Pascal, I.; Zhou, H.-
C. J. Am. Chem. Soc. 1999, 121, 6856.
(25) Cotton, F. A.; Donahue, J. P.; Lichtenberger, D. L.; Murillo, C.
A.; Villagran
(26) Cotton, F. A.; Donahue, J. P.; Gruhn, N. E.; Lichtenberger, D.
L.; Murillo, C. A.; Timmons, D. J.; Van Dorn, L. O.; Villagran, D.;
Wang, X. Inorg. Chem. 2006, 45, 201.
́
, D. J. Am. Chem. Soc. 2005, 127, 10808.
Jimen
Polyhedron 2010, 29, 232. (d) Barral, M. C.; Herrero, S.; Jimen
Aparicio, R.; Priego, J. L.; Torres, M. R.; Urbanos, F. A. J. Mol. Struct.
2008, 890, 221. (e) Barral, M. C.; Gallo, T.; Herrero, S.; Jimenez-
́
ez-Aparicio, R.; Priego, J. L.; Torres, M. R.; Urbanos, F. A.
́
́
ez-
(27) Chiarella, G. M.; Cotton, F. A.; Murillo, C. A.; Young, M. D.
Inorg. Chem. 2011, 50, 1258.
́
Aparicio, R.; Torres, M. R.; Urbanos, F. A. Chem.Eur. J. 2007, 13,
10088. (f) Chisholm, M. H.; Christou, G.; Folting, K.; Huffman, J. C.;
James, C. A.; Samuels, J. A.; Wesemann, J. L.; Wooddruff, W. H. Inorg.
Chem. 1996, 35, 3643. (g) Furakawa, S.; Kitagawa, S. Inorg. Chem.
2004, 43, 6464.
́
(28) Barral, M. C.; Herrero, S.; Jimenez-Aparicio, R.; Torres, M. R.;
Urbanos, F. A. Inorg. Chem. Commun. 2004, 7, 42.
(29) Angaridis, P.; Cotton, F. A.; Murillo, C. A.; Wang, X. Acta
Crystallogr. 2005, C61, m71.
́
(30) Barral, M. C.; Casanova, D.; Herrero, S.; Jimenez-Aparicio, R.;
(12) For additional information on substituents effects on dinuclear
paddlewheel compounds and Hammett σ constants for DAniF species,
see: Ren, T. Coord. Chem. Rev. 1998, 175, 43.
Torres, M. R.; Urbanos, F. A. Chem.Eur. J. 2010, 16, 6203.
(31) See, for example: Liu, I. P.-C.; Ren, T. Inorg. Chem. 2009, 48,
5608.
I
dx.doi.org/10.1021/ja5020647 | J. Am. Chem. Soc. XXXX, XXX, XXX−XXX