B.K. Dey et al. / Journal of Organometallic Chemistry 750 (2014) 176e184
183
Table 7
the Gaussian 03 (B3LYP/SDD-6-31G) package [56]. Electrochemical
Crystallographic data for the [Ru(LeOCH3)(CO)2Cl2] complex.
measurements were made using a CH Instruments model 600A
electrochemical analyzer. A platinum disc working electrode, a
platinum wire auxiliary electrode and an aqueous saturated
calomel reference electrode (SCE) were used in the cyclic voltam-
metry experiments. All electrochemical experiments were per-
formed under a dinitrogen atmosphere. All electrochemical data
were collected at 298 K and are uncorrected for junction potentials.
GCeMS analyses were performed using a Perkin Elmer CLARUS 680
instrument.
Empirical formula
Formula weight
Crystal system
Space group
C15H12N2O3Cl2Ru
440.24
Monoclinic
P21/n
13.4717(7)
8.5593(2)
14.9129(13)
104.929(6)
1661.53(17)
4
ꢀ
a (A)
ꢀ
b (A)
ꢀ
c (A)
b
(ꢁ)
3
ꢀ
V (A )
Z
Dcalcd (mg mꢀ3
)
1.760
4.3. Syntheses of complexes
F (000)
872
ꢀ
l
(A)
0.71073
0.03 ꢂ 0.19 ꢂ 0.19
150
1.279
10,386
crystal size (mm3)
The [Ru(LeR)(CO)2Cl2] complexes were synthesized by
following a general procedure. Specific details are given below for a
particular complex.
T (K)
m
(mmꢀ1
)
Collected reflections
[Ru(LeOCH3)(CO)2Cl2]. To
a
solution of LeOCH3 (93 mg,
Rint
0.028
4669
0.0296
0.0675
Independent reflections
0.44 mmol) in methanol (30 mL) [Ru(CO)2Cl2]n (100 mg,
0.44 mmol) was added [57], and the mixture was heated at reflux
for 2 h to yield a red solution. Evaporation of this solution gave a red
solid, which was subjected to purification by thin layer chroma-
tography on a silica plate. Using 1:3 dichloromethaneebenzene as
the eluant, a red band separated, which was extracted with
dichloromethane. Upon evaporation of the dichloromethane
extract [Ru(LeOCH3)(CO)2Cl2] was obtained as a crystalline red
solid. Yield: 67%. Anal. Calcd. for C15H12N2O3Cl2Ru: C, 40.89; H,
2.73; N, 6.36. Found: C, 40.85; H, 2.71; N, 6.40%. 1H NMR [58]: 3.87
(s, 3H); 7.02 (d, 2H, J ¼ 8.6); 7.62 (d, 2H, J ¼ 7.2); 7.73 (t, 1H, J ¼ 6.4);
8.00 (d,1H, J ¼ 7.4); 8.14 (t,1H, J ¼ 7.8); 8.47 (s, azomethine); 9.18 (d,
R1a
wR2b
Gofc
0.94
P
P
a
b
c
R1 ¼ jjFoj ꢀ j:Fcj:j= jFoj.
wR2 ¼ [S{w(F2o ꢀ F2c)2}/S{w(F2o)}]1/2
.
Gof ¼ [S(w(F2o ꢀ F2c)2)/(M ꢀ N)]1/2, where M is the number of reflections
and N is the number of parameters refine.
1979, 1601, 1510, 1475, 1440, 1258, 1202, 1105, 823, 776 and
585 cmꢀ1
.
1H, J ¼ 5.2). 13C NMR [59]: 55.5 (OCH3); 114.2 (Cix, Cxi); 124.0 (Cviii
,
4.4. X-ray crystallography
C
xii); 127.2 (Civ); 127.4 (Cii); 138.4 (Ciii); 147.1 (Cvii); 150.1 (Ci), 154.6
(Cvi); 160.0 (Cx); 163.8 (Cv); 200.0 (CO); 208.8 (CO). IR: 2053, 1976,
1602, 1505, 1480, 1445, 1210, 1109, 819, 775 and 586 cmꢀ1
[Ru(LeCH3)(CO)2Cl2]. Yield: 66%. Anal. Calcd.
15H12N2O2Cl2Ru: C, 42.43; H, 2.83; N, 6.60. Found: C, 42.39; H,
Single crystals of [Ru(LeOCH3)(CO)2Cl2] were obtained by slow
.
evaporation of solvent from
a solution of the complex in
for
dichloromethane. Selected crystal data and data collection pa-
rameters are given in Table 7. Data on the crystal were collected on
a Bruker SMART CCD diffractometer. X-ray data reduction, structure
solution and refinement were done using the SHELXS-97 and
SHELXL-97 packages [60]. The structure was solved by the direct
methods.
C
2.81; N, 6.63%. 1H NMR: 2.43 (s, 3H); 7.30 (d, 2H, J ¼ 5.2); 7.56 (d, 2H,
J ¼ 8.2); 7.74 (t, 1H, J ¼ 6.3); 8.02 (d, 1H, J ¼ 7.6); 8.14 (t, 1H, J ¼ 7.6);
8.49 (s, azomethine); 9.14 (d, 1H, J ¼ 5.1). 13C NMR: 21.1 (CH3); 121.4
(Cviii, Cxii); 127.5 (Civ); 128.8 (Cii); 129.5 (Cix, Cxi); 138.5 (Ciii); 138.9
(Cx); 147.8 (Cvii), 150.1 (Ci); 154.5 (Cvi); 164.5 (Cv); 200.0 (CO); 208.7
(CO). IR: 2061, 1973, 1607, 1502, 1473, 1442, 1205, 1108, 821, 773 and
4.5. General procedure for the CeC cross-coupling
584 cmꢀ1
[Ru(LeH)(CO)2Cl2].
.
Yield:
65%.
Anal.
Calcd.
for
In a typical run, an oven-dried 10 mL round bottom flask was
charged with a known mole percent of ruthenium catalyst, K3PO4
(1.0 mmol), p-substituted phenylboronic acid (1.25 mmol), ligand
(0.05 mmol), arylaldehyde (0.5 mmol) and 2.0 mL toluene and
0.2 mL water as solvent. The flask was placed in a preheated oil bath
at required temperature. After the specified time the flask was
removed from the oil bath and water (20 mL) added, followed by
extraction with ether (4 ꢂ 10 mL). The combined organic layers
were washed with water (3 ꢂ 10 mL), dried over anhydrous Na2SO4,
and filtered. Solvent was removed under vacuum. The residue was
dissolved in hexane and analyzed by GCMS.
C
14H10N2O2Cl2Ru: C, 40.95; H, 2.44; N, 6.83. Found: C, 40.93; H,
2.42; N, 6.85%. 1H NMR: 7.35 (d, 2H, J ¼ 7.8); 7.45 (3H)*; 7.73 (t, 1H,
J ¼ 5.4); 8.02 (d, 1H, J ¼ 7.8); 8.18 (t, 1H, J ¼ 7.3); 8.44 (s, azome-
thine); 9.22 (d, 1H, J ¼ 5.0). 13C NMR: 121.5 (Cviii, Cxii); 127.6 (Civ);
128.7 (Cii); 129.2 (Cix, Cxi); 130.1 (Cx); 138.3 (Ciii); 149.7 (Cvii), 150.4
(Ci); 154.2 (Cvi); 164.8 (Cv); 199.6 (CO); 208.2 (CO). IR: 2059, 1978,
1603, 1500, 1478, 1441, 1208, 1107, 820, 776 and 579 cmꢀ1
.
[Ru(LeCl)(CO)2Cl2]. Yield: 62%. Anal. Calcd. for C14H9N2O2Cl3Ru:
C, 37.78; H, 2.02; N, 6.30. Found: C, 37.75; H, 1.97; N, 6.35%. 1H NMR:
7.40 (d, 2H, J ¼ 8.4); 7.46 (d, 2H, J ¼ 8.4); 7.73 (t, 1H, J ¼ 5.6); 8.02 (d,
1H, J ¼ 7.6); 8.11 (t, 1H, J ¼ 7.3); 8.38 (s, azomethine); 9.20 (d, 1H,
J ¼ 5.4). 13C NMR: 122.9 (Cviii, Cxii); 127.7 (Civ); 128.8 (Cii); 129.3 (Cix,
Cxi); 135.6 (Cx); 138.5 (Ciii); 147.8 (Cvii), 150.6 (Ci); 154.3 (Cvi); 164.7
(Cv); 199.7 (CO); 208.4 (CO). IR: 2062, 1977, 1605, 1503, 1479, 1443,
Acknowledgments
1203, 1103, 818, 778 and 583 cmꢀ1
[Ru(LeNO2)(CO)2Cl2]. Yield:
C
.
The authors thank the reviewers for their constructive com-
ments, which have been very helpful in preparing the revised
manuscript. Financial assistance received from the Department of
Science and Technology, New Delhi [Grant No. SR/S1/IC-29/2009
and SR/S1/RFIC-01/2009] is gratefully acknowledged. Bikash Kali
Dey and Jayita Dutta thank the Council of Scientific and Industrial
Research, New Delhi, for their fellowship [Grant No. 09/096(0555)/
2008-EMR-I and 09/096(0702)/2011-EMR-I respectively].
60%.
Anal.
Calcd.
for
14H9N3O4Cl2Ru: C, 36.90; H, 1.98; N, 9.23. Found: C, 36.88; H, 1.97;
N, 9.26%. 1H NMR: 7.45 (d, 2H, J ¼ 8.5); 7.59 (d, 2H, J ¼ 8.3); 7.73 (t,
1H, J ¼ 5.8); 8.04 (d, 1H, J ¼ 7.5); 8.15 (t, 1H, J ¼ 7.2); 8.36 (s, azo-
methine); 9.21 (d, 1H, J ¼ 5.2). 13C NMR: 122.4 (Cviii, Cxii); 126.6
(Civ); 127.4 (Cii); 128.1 (Cix, Cxi); 138.2 (Cx); 138.6 (Ciii); 149.3 (Cvii),
150.5 (Ci); 154.7 (Cvi); 164.8 (Cv); 200.1 (CO); 208.6 (CO). IR: 2065,