T.K. Mondal et al. / Inorganic Chemistry Communications 13 (2010) 273–277
277
(b) B.G. Chand, U.S. Ray, G. Mostafa, T.-H. Lu, C. Sinha, Polyhedron 23 (2004)
1669.
[7] E. Ambundo, L.A. Ochrymowycz, D.B. Rorabacher, Inorg. Chem. 40 (2001) 5133.
[8] U.S. Ray, D. Banerjee, G. Mostafa, T.-H. Lu, C. Sinha, New J. Chem. 28 (2004)
1432.
for 2a, and ꢀ13 6 h 6 13, ꢀ14 6 k 6 14, ꢀ20 6 l 6 20 for 3b. Reflection data
were recorded using the scan technique. Data were corrected for Lorentz
polarization effects and for linear decay. Semi-empirical absorption
corrections based on -scans were applied. The structure were solved by
direct method using SHELXS-97 [G. M. Sheldrick, SHELXS-97, University of
Gottingen, Germany, 1997] and successive difference Fourier syntheses. All
non-hydrogen atoms were refined anisotropically. The hydrogen atoms were
fixed geometrically and refined using the riding model. All calculation were
carried out using SHELXL-97 [G.M. Sheldrick, SHELXL 97, University of
Gottingen, Germany, 1997], ORTEP-32 [L.J. Farrugia, ORTEP-3 for windows, J.
Appl. Cryst. 30 (1997) 565], and PLATON-99 [A.L. Spek, PLATON, The
Netherlands, 1999] programs.
x
w
[9] D. Banerjee, U.S. Ray, S.K. Jasimuddin, J.-C. Liou, T.-H. Lu, C. Sinha, Polyhedron
25 (2006) 1299.
[10] Synthesis of cis-(CO)-trans-(Cl)-[Ru(SMeaaiNMe)(CO)2Cl2](2a): [Ru(CO)2(Cl)2]n
(0.31 g, 1.4 mmol) was dissolved in hot ethanol (30 ml). An ethanolic solution
of SMeaaiNMe (1a) (0.35 g, 1.5 mmol) was added and refluxed for 2 h under N2
atmosphere. The solution was cooled to room temperature. Under slow
evaporation of the solvent brown crystalline product was left. The product was
recrystallized from CH2Cl2–MeOH solution. The yield was 0.36 g (62%).
Microanalytical data: Calc. (found). For C13H12N4O2Cl2Ru (2a): C,
[16] (a) B.K. Ghosh, A. Chakravorty, Coord. Chem. Rev. 95 (1989) 239;
(b) T.K. Misra, D. Das, C. Sinha, P.K. Ghosh, C.K. Pal, Inorg. Chem. 37 (1998)
1672;
36.45(36.36); H, 2.80(2.79); N, 13.08(13.05). IRexp (KBr) (cmꢀ1):
2066, 2004, (C@N) 1547, (N@N) 1373, (Ru–Cl) 342. IRtheo (b3lyp/sdd)
(cmꢀ1): (Ru–Cl) 331. E1/2(RuII/
(CO) 2023, 2072, (C@N) 1575, (N@N) 1407,
RuIII), V (
Ep, mV): 1.26(120); E1/2 (L), V (
m(cis-CO)
m
m
m
(c) S. Serroni, S. Campagna, F. Puntoriero, C.D. Pietro, N.D. Mcclenaghan, F.
Loiseau, Chem. Soc. Rev. 30 (2001) 367;
(d) P. Byabartta, J. Dinda, P.K. Santra, C. Sinha, K. Panneerselvam, F.-L. Liao, T.-
H. Lu, J. Chem. Soc., Dalton Trans. (2001) 2825;
(e) R.E. Shepherd, Coord. Chem. Rev. 247 (2003) 147;
(f) S. Patra, B. Sarkar, S. Maji, J. Fiedler, F.A. Urbanos, R. Jimenez-Aparicio, W.
Kaim, G.K. Lahiri, Chem. – A: Eur. J. 12 (2006) 489.
m
m
m
m
D
D
Ep, mV): ꢀ0.45(80), ꢀ1.00(100),
ꢀ1.44(150). The compound 2b was prepared following the same procedure as
2a. The yield was 65%. Microanalytical data: Calc. (found), for
C15H16N4O2Cl2Ru (2b): C, 39.47(39.42); H, 3.51(3.51); N, 12.28(12.26). IRexp
(KBr) (cmꢀ1):
E1/2(RuII/RuIII),
ꢀ0.98(100), ꢀ1.38(150).
m
(cis-CO) 2062, 1998,
m
(C@N) 1544,
m
(N@N) 1377,
m(Ru–Cl) 341.
Ep, mV): ꢀ0.44(80),
V
(
D
Ep, mV): 1.22(120); E1/2 (L),
V
(D
[17] (a) T.K. Mondal, J.-S. Wub, T.-H. Lu, S.K. Jasimuddin, C. Sinha, J. Organomet.
Chem. 694 (2009) 3518;
(b) T.K. Mondal, S.K. Sarker, P. Raghavaiah, C. Sinha, Polyhedron 27 (2008)
3020.
[18] J.E. Huheey, E.A. Keiter, R.L. Keiter, Inorganic Chemistry Harper Collins, fourth
ed., Addison-Wesley Publishing Company, 2000.
[11] Synthesis of trans-(Cl)-[Ru(SMeaaiNMe)(CO)Cl2] (3a); A 0.5 g (2.26 mmol) of
[Ru(CO)2Cl2]n and 0.58 g (2.5 mmol) of SMeaaiNMe were dissolved in 40 mL
acetonitrile. Freshly sublimed Me3NO (0.07 g) was added under dry N2
environment. The solution was then refluxed for 3 h. The bright brown
solution changed to green. Under slow evaporation of the solvent a dark green
crystalline product was left. It was then dried and chromatographed and a
dark green band was eluted by C6H6-acetonitrile (5:1, v/v) and evaporated in
air. The yield was 0.66 g (68%). Microanalytical data: Calc. (found). For
C12H12N4OCl2Ru (3a): C, 36.00(35.92); H, 3.00(2.99); N, 14.00(13.98). IRexp
[19] J. Otsuki, K. Suwa, K. Narutaki, C. Sinha, I. Yoshikawa, K. Araki, J. Phys. Chem. A
109 (2005) 8064;
P. Bhunia, B. Baruri, U.S. Ray, C. Sinha, S. Das, J. Cheng, T.-H. Lu, Transit. Met.
Chem. 31 (2006) 310.
[20] Full geometry optimizations were carried out using the density functional
theory method at the (R)B3LYP level for 2a and 3b [C. Lee, W. Yang, R.G. Parr,
Phys. Rev. B 37 (1988) 785]. Elements except ruthenium were assigned a 6-
311G(d) basis set in these calculation. The SDD basis set with effective core
potential was employed for ruthenium atom [P. Fuentealba, H. Preuss, H. Stoll,
L.V. Szentpaly, Chem. Phys. Lett. 89 (1989) 418]. All calculation were
performed with Gaussian03 program package [M.J. Frisch et al., Gaussian 03,
Revision D.01, Gaussian Inc., Wallingford CT, 2004] with the aid of the
GaussView visualization program. Natural bond orbital analyses were
performed using the NBO 3.1 module of Gaussian03 [NBO Version 3.1, E.D.
Glenening, A.E. Reed, J.E. Carpenter, F. Weinhold]. Vertical electronic
excitations based on B3LYP optimized geometries was computed using the
time-dependent density functional theory (TDDFT) formalism [R.
Bauernschmitt, R. Ahlrichs, Chem. Phys. Lett. 256 (1996) 454] in
dichloromethane using conductor-like polarizable continuum model (CPCM)
[V. Barone, M. Cossi, J. Phys. Chem. A 102 (1998) 1995]. GaussSum [N.M.
O’Boyle, A.L. Tenderholt, K.M. Langner, J. Comput. Chem. 29 (2008) 839] was
used to calculate the fractional contributions of various groups to each
molecular orbital.
(KBr) (cmꢀ1):
E1/2(RuII/RuIII),
m
V
(cis-CO) 1995,
m
(C@N) 1553,
m
(N@N) 1391,
m(Ru–Cl) 343.
(D
Ep, mV): 0.78(105); E1/2 (L), V (D
Ep, mV): ꢀ0.48(90),
ꢀ1.10(115), ꢀ1.46(140). The complex 3b was prepared following the same
procedure as 3a. The yield was 69%. Microanalytical data: Calc. (found), for
C14H16N4O2Cl2Ru (3b): C, 39.25(39.12); H, 3.74(3.72); N, 13.08(13.05). IRexp
(KBr) (cmꢀ1):
(b3lyp/sdd) (cmꢀ1):
E1/2(RuII/RuIII),
m
(cis-CO) 1991,
(CO) 2015,
Ep, mV): 0.76(105); E1/2 (L), V (D
m
(C@N) 1555,
m
(N@N) 1396,
(N@N) 1400,
Ep, mV): ꢀ0.49(90),
m
(Ru–Cl) 340. IRtheo
m
m
(C@N) 1566,
m
m
(Ru–Cl) 324.
V
(D
ꢀ1.12(110), ꢀ1.48(140).
[12] M.M. Khodaei, K. Bahrami, A. Karimi, Synthesis (2008) 1682;
M. Mba, L.J. Prins, G. Licini, Org. Lett. 9 (2007) 21.
[13] K.K. Sarker, B.G. Chand, K. Suwa, J. Cheng, T.-H. Lu, J. Otsuki, C. Sinha, Inorg.
Chem. 46 (2007) 670;
K.K. Sarker, d. Sardar, K. Suwa, J. Otsuki, C. Sinha, Inorg. Chem. 46 (2007) 8291;
P. Pratihar, T.K. Mondal, A.K. Patra, C. Sinha, Inorg. Chem. 48 (2009) 2760.
[14] T. Yutaka, M. Kurihara, .H. Nishihara, Mol. Cryst. Liquid Cryst. 343 (2000) 193;
T. Yutaka, L. Mori, M. Kurihara, J. Mizutani, K. kubo, S. Furusho, K. Matsumura,
N. Tamai, H. Nishihara, Inorg. Chem. 40 (2001) 4986.
[15] Single crystal data collections were performed with an automated Bruker
SMART APEX CCD diffractometer. Unit cell parameters were determined from
least-squares refinement of setting angles (h) within the range
1.45 6 h 6 25.98° (2a) and 2.00 6 h 6 28.09° (3b). Out of 5797 collected data
[21] Electrochemical measurements were performed using computer-controlled
PAR model 250 VersaStat electrochemical instruments with Pt-disk milli
working electrode, Pt-auxiliary and SCE as reference. All measurements were
carried out under nitrogen environment at 298 K in acetonitrile using
[nBu4N][ClO4] as supporting electrolyte at 50 mV Sꢀ1 scan rate.
3241 for 2a, and 14823 collected data 4090 for 3b with I > 2
r (I) were used for
structure solution. The hkl ranges are ꢀ9 6 h 6 9, ꢀ10 6 k 6 10, ꢀ17 6 l 6 17