Organometallics
Article
Preparation of [Cp*Ru(μ-1κ3SSO:2κ2SS-opdt)Ni(dppe)][PF6]
(4). NiCl2(dppe) (210 mg, 0.4 mmol) was added to a stirred
suspension of Li2(opdt) in THF (10 mL), prepared by the reaction of
nBuLi (0.36 mL, 2.2 M solution in n-hexane, 0.8 mmol) and
AUTHOR INFORMATION
Corresponding Author
■
O(CH2CH2SH)2 (55 mg, 0.4 mmol) at 0 °C, and the solution was
stirred at room temperature for 1 h. Then, the red solution gradually
turned into a yellow-green solution when [Cp*Ru(MeCN)3][PF6]
(202 mg, 0.4 mmol) was added. All volatiles were removed under
vacuum, and the residue was washed with n-hexane three times,
extracted with CH2Cl2, and then dried in vacuo. The product,
[Cp*Ru(μ-1κ3SSO:2κ2SS-opdt)Ni(dppe)][PF6] (4; 311 mg, 0.32
mmol, 80%), was obtained as a brownish yellow powder. Crystals
suitable for X-ray diffraction were obtained from a saturated CH2Cl2
Notes
The authors declare no competing financial interest.
ACKNOWLEDGMENTS
■
This work was supported by the National Natural Science
Foundation of China (Nos. 21231003, 21571026), the Program
for Changjiang Scholars and Innovative Research Team in
University (No. IRT13008), and the “111” project of the
Ministry of Education of China.
1
solution layered with n-hexane at room temperature. H NMR (400
MHz, CD2Cl2, ppm): δ 0.95 (s, 15 H, Cp*-CH3), 1.50 (m, 4 H,
Ph2P(CH2)2PPh2-CH2), 2.66−2.71 (m, 8 H, opdt-H), 7.43−7.57 (m,
20 H, Ph-H). ESI-HRMS: calcd for [4 − PF6]+ 829.0944; found
829.0923. Anal. Calcd for C40H47RuNiOP2S2: C, 57.91; H, 5.71; S,
7.73. Found: C, 57.82; H, 5.64; S, 7.65.
REFERENCES
■
(1) Cammack, R.; Frey, M.; Robson, R. Hydrogen as a Fuel: Learning
from Nature; Taylor & Francis: London, 2001.
Preparation of [Cp*Fe(t-CO)(μ-1κ2SS:2κ3SSO-opdt)Ni-
(dppe)][PF6] (5). Under 1 atm of CO, a solution of [Cp*Fe(μ-
1κ3SSO:2κ2SS-opdt)Ni(dppe)][PF6] (2; 464 mg, 0.5 mmol) in THF
(10 mL) was stirred at room temperature for 20 min. During this time,
the solution changed gradually from brownish green to brownish
yellow. All volatiles were removed under vacuum, and the residue was
washed with n-hexane three times and then dried in vacuo. The
product, [Cp*Fe(t-CO)(μ-1κ2SS:2κ3SSO-opdt)Ni(dppe)][PF6] (5;
343 mg, 0.35 mmol, 70%), was obtained as a brownish yellow
powder. Crystals of 5 suitable for X-ray diffraction were obtained from
a saturated CH2Cl2 solution layered with n-hexane at room
(2) Lubitz, W.; Ogata, H.; Rudiger, O.; Reijerse, E. Chem. Rev. 2014,
114, 4081−4148.
̈
(3) Volbeda, A.; Charon, M.-H.; Piras, C.; Hatchikian, E. C.; Frey,
M.; Fontecilla-Camps, J. C. Nature 1995, 373, 580−587.
(4) Volbeda, A.; Garcin, E.; Piras, C.; De Lacy, A. L.; Fernandez, V.
M.; Hatchikian, E. C.; Frey, M.; Fontecilla-Camps, J. C. J. Am. Chem.
Soc. 1996, 118, 12989−12996.
(5) Fontecilla-Camps, J. C.; Volbeda, A.; Cavazza, C.; Nicolet, Y.
Chem. Rev. 2007, 107, 4273−4303.
(6) Ogata, H.; Nishikawa, K.; Lubitz, W. Nature 2015, 520, 571−585.
(7) (a) Tard, C.; Pickett, C. J. Chem. Rev. 2009, 109, 2245−2274.
(b) Gloaguen, F.; Rauchfuss, T. B. Chem. Soc. Rev. 2009, 38, 100−108.
1
temperature. H NMR (400 MHz, CD2Cl2, ppm): δ 1.51 (s, 15 H,
Cp*-CH3), 1.80−3.40 (m, 4 H, Ph2P(CH2)2PPh2-CH2), 2.67−2.81
́
(c) Capon, J.; Gloaguen, F.; Petillon, F. Y.; Schollhammer, P.;
(m, 8 H, opdt-H), 7.55−7.93 (m, 20 H, Ph-H). IR (KBr): νCO 1904
̃
Talarmin, J. Coord. Chem. Rev. 2009, 253, 1476−1494. (d) Simmons,
T. R.; Berggren, G.; Bacchi, M.; Fontecave, M.; Artero, V. Coord.
Chem. Rev. 2014, 270−271, 127−150. (e) Rauchfuss, T. B. Acc. Chem.
Res. 2015, 48, 2107−2116.
cm−1. ESI-HRMS: calcd for [5 − PF6]+ 811.1196; found 811.1184.
Anal. Calcd For C41H47FeNiO2P2S2: C, 60.61; H, 5.83; S, 7.89. Found:
C, 60.52; H, 5.90; S, 7.97.
Preparation of [Cp*Ru(t-CO)(μ-1κ2SS:2κ3SSO-opdt)Ni-
(dppe)][PF6] (6). Under 1 atm of CO, a solution of [Cp*Ru(μ-
1κ3SSO:2κ2SS-opdt)Ni(dppe)][PF6] (6; 292 mg, 0.3 mmol) in THF
(10 mL) was stirred at room temperature for 12 h. During this time,
the solution gradually changed from brownish green to brownish
yellow. All volatiles were removed under vacuum, and the residue was
washed with n-hexane three times and then dried in vacuo. The
product, [Cp*Ru(t-CO)(μ-1κ2SS:2κ3SSO-opdt)Ni(dppe)][PF6] (6;
220 mg, 0.22 mmol, 73%), was obtained as a brownish-yellow
powder. Crystals of 6 suitable for X-ray diffraction were obtained from
a saturated CH2Cl2 solution layered with n-hexane at room
(8) (a) Marr, A. C.; Spencer, D. J. E.; Schroder, M. Coord. Chem. Rev.
̈
2001, 219−221, 1055−1074. (b) Bouwman, E.; Reedijk, J. Coord.
Chem. Rev. 2005, 249, 1555−1581. (c) Ohki, Y.; Tatsumi, K. Eur. J.
Inorg. Chem. 2011, 2011, 973−985.
(9) (a) Canaguier, S.; Artero, V.; Fontecave, M. Dalton Trans. 2008,
315−325. (b) Barton, B. E.; Whaley, M.; Rauchfuss, T. B.; Gray, D. L.
J. Am. Chem. Soc. 2009, 131, 6942−6943. (c) Barton, B. E.; Rauchfuss,
T. B. J. Am. Chem. Soc. 2010, 132, 14877−14885. (d) Canaguier, S.;
́
Field, M.; Oudart, Y.; Pecaut, J.; Fontecave, M.; Artero, V. Chem.
Commun. 2010, 46, 5876−5878. (e) Weber, K.; Kramer, T.; Shafaat,
̈
H. S.; Weyhermuller, T.; Bill, E.; van Gastel, M.; Neese, F.; Lubitz, W.
̈
1
temperature. H NMR (400 MHz, CD2Cl2, ppm): δ 1.67 (s, 15 H,
J. Am. Chem. Soc. 2012, 134, 20745−20755.
Cp*-CH3), 2.82−3.37 (m, 4 H, Ph2P(CH2)2PPh2-CH2), 2.15−2.42
(10) (a) Ogo, S.; Kabe, R.; Uehara, K.; Kure, B.; Nishimura, T.;
Menon, S. C.; Harada, R.; Fukuzumi, S.; Higushi, Y.; Ohhara, T.;
Tamada, T.; Kuroki, R. Science 2007, 316, 585−587. (b) Ogo, S.;
Ichikawa, K.; Kishima, T.; Matsumoto, T.; Nakai, H.; Kusaka, K.;
Ohhara, T. Science 2013, 339, 682−684. (c) Manor, B. C.; Rauchfuss,
T. B. J. Am. Chem. Soc. 2013, 135, 11895−11900.
(m, 8 H, opdt-H), 7.59−8.12 (m, 20 H, Ph-H). IR (KBr): νCO 1903
̃
cm−1. ESI-HRMS: calcd for [6 − PF6]+ 857.0894; found 857.0716.
Anal. Calcd for C41H47RuNiO2P2S2: C, 57.42; H, 5.52; S, 7.48. Found:
C, 57.48; H, 5.44; S, 7.41.
(11) (a) Darensbourg, D. J.; Reibenspies, J. H.; Lai, C.-H.; Lee, W.-
Z.; Darensbourg, M. Y. J. Am. Chem. Soc. 1997, 119, 7903−7904.
(b) Lai, C.-H.; Lee, W.-Z.; Miller, M. L.; Reibenspies, J. H.;
Darensbourg, D. J.; Darensbourg, M. Y. J. Am. Chem. Soc. 1998,
120, 10103−10114.
(12) Zhu, W.; Marr, A. C.; Wang, Q.; Neese, F.; Spencer, D. J. E.;
Blake, A. J.; Cooke, P. A.; Wilson, C.; Schroder, M. Proc. Natl. Acad.
Sci. U. S. A. 2005, 102, 18280−18285.
(13) (a) Lamle, S. E.; Albracht, S. P. J.; Armstrong, F. A. J. Am. Chem.
Soc. 2005, 127, 6595−6604. (b) Lubitz, W.; Reijerse, E.; van Gastel, M.
Chem. Rev. 2007, 107, 4331−4365. (c) Ogata, H.; Lubitz, W.; Higuchi,
Y. Dalton Trans. 2009, 7577−7587.
(14) (a) van der Zwaan, J. W.; Coremans, J. M. C. C.; Bouwens, E. C.
M.; Albracht, S. P. J. Biochim. Biophys. Acta, Protein Struct. Mol.
Enzymol. 1990, 1041, 101−110. (b) Bagley, K. A.; van Garderen, C. J.;
Chen, M.; Duin, E. C.; Albracht, S. P. J.; Woodruff, W. H. Biochemistry
ASSOCIATED CONTENT
■
S
* Supporting Information
The Supporting Information is available free of charge on the
̈
X-ray crystallographic data and spectroscopic data (PDF)
X-ray crystallographic data for 1 (CIF)
X-ray crystallographic data for 2 (CIF)
X-ray crystallographic data for 3 (CIF)
X-ray crystallographic data for 4 (CIF)
X-ray crystallographic data for 5 (CIF)
X-ray crystallographic data for 6 (CIF)
F
Organometallics XXXX, XXX, XXX−XXX