RSC Advances
Paper
taken from a H2 cylinder (Soxal, 99.99%). The Faraday yield of
84 ꢂ 12% was determined by the average of three readings of
[H2 detected]/[electrons used for electrolysis] ratios.
Acknowledgements
This work was supported by a NUS research grant (143-000-553-
112).
Synthesis of Mn2(CO)8(m-SePh)2 (1)
Notes and references
The synthesis of complex 1 has already been described in ref. 19.
1 S. U. M. Khan, M. Al-Shahry and W. B. Ingler, Science, 2002,
297, 2243–2245.
2 N. S. Lewis and D. G. Nocera, Proc. Natl. Acad. Sci. U. S. A.,
2006, 103, 15729–15735.
Synthesis of Mn2(CO)4(m-CO)(m-SePh)2(L)2 (2, L ¼ PBu3, tri-n-
butylphosphine)
3 H. B. Gray, Nat. Chem., 2009, 1, 7.
4 R. Eisenberg, Science, 2009, 324, 44–45.
Mn2(CO)8(m-SePh)2 (32.3 mg, 0.05 mmol) and tri-n-butylphos-
phine (20.2 mg, 0.10 mmol) were added to a 25 mL of hexane
and subjected to photolysis for 15 min. Suitable crystal of 2 was
grown by dissolving them in dichloromethane–hexane and
stored at low temperature for days. Yield: 31 mg, 64.0%. Anal.
calc. for C41H64Mn2O5P2Se2: C, 50.94; H, 6.67. Found: C, 51.22;
H, 7.05. IR nCO (CH2Cl2): 1904(s), 1945(s), 2010(vs). 1H NMR
d(CDCl3): 0.73 (t, 10H ,–CH3), 0.96–1.90 (m, 18H, –P(CH2)3).
7.13–7.38 (m, 10H, –Ph).
5 (a) C. Tard and C. J. Pickett, Chem. Rev., 2009, 109, 2245–
2274; (b) J. Fritsch, P. Scheerer, S. Frielingsdorf,
S. Kroschinsky, B. Friedrich, O. Lenz, C. M. Spahn and
C. M. T. Spahn, Nature, 2011, 479, 249–252.
6 Y. Higuchi, H. Ogata, K. Miki, N. Yasuoka and T. Yagi,
Structure, 1999, 7, 549–556.
7 E. Garcin, X. Vernede, E. C. Hatchikian, A. Volbeda, M. Frey
and J. C. Fontecilla-Camps, Structure, 1999, 7, 557–566.
8 (a) Z. Li, Y. Ohki and K. Tatsumi, J. Am. Chem. Soc., 2005, 127,
8950–8951; (b) S. Ogo, K. Ichikawa, T. Kishima,
T. Matsumoto, H. Nakai, K. Kusaka and T. Ohhara, Science,
2013, 339, 682–684.
9 (a) L. C. Sun, B. Akermark and S. Ott, Coord. Chem. Rev.,
2005, 249, 1653–1663; (b) A. Parkin, G. Goldet, C. Cavazza,
J. C. Fontecilla-Camps and F. A. Armstrong, J. Am. Chem.
Soc., 2008, 130, 13410–13416; (c) F. Gloaguen and
T. B. Rauchfuss, Chem. Soc. Rev., 2009, 38, 100–108; (d)
Synthesis of Mn(CO)4(m-SePh)2Mn(CO)3(Py) (3, Py ¼ pyridine)
Mn2(CO)10 (100 mg, 0.26 mmol), diphenyl diselenide (163 mg,
0.52 mmol) and pyridine (82 mg, 1.04 mmol) were added to a
50 mL of hexane and subjected to photolysis for 3 h. Suitable
crystals of 3 were grown by dissolving them in dichloro-
methane–hexane and stored at low temperature for days.
Yield: 107 mg, 58.5% (based on Mn2(CO)10). Anal. calc. for
C
24H15Mn2NO7Se2: C, 41.35; H, 2.17. Found: C, 41.62; H, 2.26.
¨
A. C. Marr, D. J. E. Spencer and M. Schroder, Coord. Chem.
IR nCO (CH2Cl2): 1912(s), 1934(s), 2001(s), 2020(vs). 1H NMR
Rev., 2001, 219, 1055–1074; (e) M. Y. Darensbourg,
E. J. Lyon and J. J. Smee, Coord. Chem. Rev., 2000, 206,
533–561.
d(CDCl3): 7.29–7.59 (m, 10H, from Ph, 5H, pyridine).
10 (a) L. C. Song, Acc. Chem. Res., 2005, 38, 21–28; (b)
G. A. N. Felton, C. A. Mebi, B. J. Petro, A. K. Vannucci,
D. H. Evans, R. S. Glass and D. L. Lichtenberger, J.
Organomet. Chem., 2009, 694, 2681–2699.
11 M. Wang, L. Chen and L. Sun, Energy Environ. Sci., 2012, 5,
6763–6778.
Synthesis of Mn(CO)3(SePh) (DPPP) (4, DPPP ¼ 1,3-
bis(diphenylphosphino)propane)
Mn2(CO)10 (100 mg, 0.26 mmol), diphenyl diselenide (163 mg,
0.52 mmol) and 1,3-Bis(diphenylphosphino)propane(219 mg,
0.52 mmol) were added to a 50 mL of hexane and subjected to
photolysis for 3 h. Suitable crystals of 4 were grown by dissolv-
ing them in dichloromethane and stored at room temperature
for days. Yield: 193 mg, 52.4% (based on Mn2(CO)10). Anal. calc.
for C36H31MnO3P2Se: C, 61.12; H, 4.42. Found: C, 61.45; H, 4.50.
˚
12 S. Ott, M. Kritikos, B. Akermark, L. Sun and R. Lomoth,
Angew. Chem., Int. Ed., 2004, 116, 1024–1027.
13 L. C. Song, J. P. Li, Z. J. Xie and H. B. Song, Inorg. Chem.,
2013, 52, 11618–11626.
1
IR nCO (CH2Cl2): 1904(s), 1945(s), 2010(vs). H NMR d(CDCl3):
€
€
14 M. K. Harb, U. P. Apfel, J. Kubel, H. Gorls, G. A. N. Felton,
T. Sakamoto, D. H. Evans, R. S. Glass, D. L. Lichtenberger
and M. El-Khateeb, Organometallics, 2009, 28, 6666–6675.
1.50–2.80 (m, 6H, CH2), 6.78–7.72 (m, 15H, –Ph).
€
15 M. K. Harb, T. Niksch, J. Windhager, H. Gorls, R. Holze,
Synthesis of Mn(CO)3(O2CCF3)(DPPP) (5)
L. T. Lockett, N. Okumura, D. H. Evans, R. S. Glass and
50 mg Mn(CO)3(SePh) (DPPP) was dissolved in CH2Cl2 and
D. L. Lichtenberger, Organometallics, 2009, 28, 1039–1048.
equivalent CF3COOH was added to generate 5. Suitable crystal 16 C. Wombwell and E. Reisner, Dalton Trans., 2014, 43, 4483–
of complexes 3 was grown by dissolving them in dichloro- 4493.
methane and stored at room temperature for days. Yield: 45 mg, 17 K. Hou, K. H. T. Poh and W. Y. Fan, Chem. Commun., 2014,
89.5%. Anal. calc. for C32H26F3MnO5P2: C, 57.85; H, 3.94. 50, 6630–6632.
Found: C, 58.03; H, 4.15. IR nCO (CH2Cl2): 1918(s), 1967(s), 18 K. Hou and W. Y. Fan, Dalton Trans., 2014, 43, 16977–16980.
1
2035(vs). H NMR d(CDCl3): 1.31–2.71 (m, 6H,CH2). 7.31–7.43 19 E. W. Abel, B. C. Crosse and G. V. Hutson, J. Chem. Soc. A,
(m, 10H, –Ph).
1967, 2014–2017.
39308 | RSC Adv., 2015, 5, 39303–39309
This journal is © The Royal Society of Chemistry 2015