50
R.N. Prabhu, R. Ramesh / Journal of Organometallic Chemistry 718 (2012) 43e51
4
.3.3. [Ru(L3)(CO)(PPh
Colour: Yellow brown; Yield: 64 mg, 68%; M.p.: 242e244
with decomposition); Anal. Calc. for 41BrN
1020.08 g mol ): C, 64.71; H, 4.05; N, 2.74. Found: C, 64.80; H,
3
)
2
] (R ¼ Br; E ¼ P) (3)
4.3.8. [Ru(L4)(CO)(AsPh
3
)
2
] (R ¼ OCH
3
; E ¼ As) (8)
ꢁ
ꢁ
C
C
Colour: Yellow brown; Yield: 73 mg, 75%; M.p.: 241e243
(
(
C
55
H
2
O
3
P
2
Ru
(with decomposition); Anal. Calc. for
56 2 2 4
C H44As N O Ru
ꢀ
1
ꢀ1
(1059.87 g mol ): C, 63.46; H, 4.18; N, 2.64. Found: C, 63.49; H,
ꢀ1
ꢀ1
4
.08; N, 2.79. IR (KBr, cm ): 1593 s
n
(C
]
NeN
]
C), 1439 s
O). H NMR (400 MHz, DMSO-d ) (
0.4 (s, 1H, CH]N), 8.4e7.2 (m, 40H, aromatic). C NMR (100 MHz,
DMSO-d ) ( ppm): 205.19 (RueCO), 166.54 (N]CeO), 155.47
CH]N), 153.06, 139.35, 136.83, 134.43, 132.93, 131.12, 130.48,
n
(PPh3)
,
4.21; N, 2.64. IR (KBr, cm ): 1593 s
n
(C
]
NeN
]
C), 1439 s
) (
10.4 (s, 1H, CH]N), 8.4e7.1 (m, 40H, aromatic), 3.9 (s, 3H, OCH
(AsPh3)
n ,
1
1
1259 m
n(CeO),1942 s
n
(C
^
6
d
ppm):
1259 m
n
(CeO),1942 s
n
(C
^
O). H NMR (400 MHz, DMSO-d
6
d
ppm):
).
6
C NMR (100 MHz, DMSO-d ) (d ppm): 205.07 (RueCO), 165.43
13
1
3
13
6
d
(
(N]CeO), 163.37, 154.73 (CH]N), 153.50, 138.32, 136.42, 135.53,
1
29.85, 129.13, 128.80, 128.28, 127.15, 126.29, 123.69, 117.26, 112.42.
133.71, 131.92, 130.23, 129.07, 128.09, 126.76, 126.22, 123.07,
3
ꢀ1
ꢀ1
UVevis (CH
3
CN,
lmax/nm;
3 /dm mol
cm ): 425 (4130),
117.20, 114.05, 112.29, 56.27. UVevis (CH
3
CN,
lmax/nm;
3
ꢀ1
ꢀ1
3
21(10,480), 245(15,140).
3 /dm mol cm ): 412(3960), 316(9310), 242(14,560).
4
.3.4. [Ru(L4)(CO)(PPh
Colour: Yellow brown; Yield: 64 mg, 72%; M.p.: 244e246
with decomposition); Anal. Calc. for
3
)
2
] (R ¼ OCH
3
; E ¼ P) (4)
4.4. X-ray crystallography
ꢁ
C
(
C
56
H
44
N
2
O
4
P
2
Ru
3 2
Single crystals of [Ru(L2)(CO)(PPh ) ] (2) suitable for X-ray
ꢀ1
(
971.98 g mol ): C, 69.20; H, 4.56; N, 2.88. Found: C, 69.40; H,
diffraction analysis were obtained by slow evaporation of
chloroformemethanol solution of the complex at room tempera-
ture. The data collection was carried out using Bruker AXS Kappa
APEX II single crystal X-ray diffractometer using monochromated
ꢀ
1
4
.62; N, 2.84. IR (KBr, cm ): 1606 s
n
(C
]
NeN
]
C), 1440 s
n
(PPh3)
,
)
1
1252 m
n
(CeO), 1942 s
n
(C
^
O)
.
H NMR (400 MHz, DMSO-d
6
(
d ppm): 10.5 (s, 1H, CH]N), 8.3e7.1 (m, 40H, aromatic), 3.8 (s,
13
3
H, OCH
3
). C NMR (100 MHz, DMSO-d
6
) (
d
ppm): 205.27
Mo K
a
radiation (kI ¼ 0.71073 Å). The absorption corrections were
(
1
1
RueCO), 165.63 (N]CeO), 163.27, 154.73 (CH]N), 153.60,
38.32, 136.55, 135.43, 133.61, 131.66, 130.33, 129.17, 128.09,
26.86, 126.12, 123.02, 117.60, 114.05, 112.20, 56.37. UVevis
performed by multi-scan method using SADABS software [54].
Corrections were made for Lorentz and polarization effects. The
structures were solved by SIR92 [55] and refined by full-matrix
3
ꢀ1
ꢀ1
2
(
CH
3
CN,
l
max/nm;
3
/dm mol
cm ): 414(4010), 314(9380),
least squares on F using SHELXL 97 [56]. All non-hydrogen atoms
2
40(14,640).
were refined anisotropically and the hydrogen atoms in these
structures were located from the difference Fourier map and con-
strained to the ideal positions in the refinement procedure. The unit
cell parameters were determined by the method of difference
vectors using reflections scanned from three different zones of the
4
.3.5. [Ru(L1)(CO)(AsPh
Colour: Yellow brown; Yield: 65 mg, 69%; M.p.: 236e238
with decomposition); Anal. Calc. for
3
)
2
] (R ¼ H; E ¼ As) (5)
ꢁ
C
(
C
55
H
42As
2
N
2
O
3
Ru
ꢀ1
(
1029.85 g mol ): C, 64.14; H, 4.11; N, 2.72. Found: C, 64.08; H,
reciprocal lattice. The intensity data were measured using
u
and 4
ꢀ
1
ꢁ
4
.16; N, 2.78. IR (KBr, cm ): 1599 s
n
(C
]
NeN
]
C), 1446 s
n
(AsPh3)
,
)
scan with a frame width of 0.5 . Frame integration and data
reduction were performed using the Bruker SAINTePlus (Version
7.06a) software [57].
1
1263 m
n
(CeO), 1942 s
n
(C
^
O)
.
H NMR (400 MHz, DMSO-d
6
1
3
(
(
1
1
d
ppm): 10.4 (s, 1H, CH]N), 8.4e7.0 (m, 41H, aromatic). C NMR
100 MHz, DMSO-d ) ( ppm): 204.07 (RueCO), 167.73 (N]CeO),
57.16 (CH]N), 153.86, 139.23, 136.05, 134.18, 132.73, 131.30,
30.23, 129.80, 129.12, 128.77, 128.02, 127.31, 126.72, 123.27, 118.85,
6
d
4.5. Typical procedure for transfer hydrogenation of ketones
3
ꢀ1
ꢀ1
112.79. UVevis (CH
3
CN,
lmax/nm;
3
/dm mol cm ): 416(3970),
In an oven-dried round bottom flask, were placed ketone
316(7980), 242(14,910).
(2.4 mmol), catalyst (3 mmol), base (12 mmol), internal standard (m-
xylene, 30
m
L, 0.24 mmol) and i-PrOH (5 mL) at room temperature.
ꢁ
4
.3.6. [Ru(L2)(CO)(AsPh
Colour: Yellow brown; Yield: 72 mg, 74%; M.p.: 247e249
with decomposition); Anal. Calc. for ClN
1064.29 g mol ): C, 62.07; H, 3.88; N, 2.63. Found: C, 62.23; H,
3
)
2
] (R ¼ Cl; E ¼ As) (6)
The reaction mixture was heated at 82 C for the required reaction
time under an atmosphere of nitrogen. Aliquots (0.2 mL) were
taken at fixed time and the catalyst removed as precipitate from the
reaction mixture by the addition of diethyl ether. The organic layer
was neutralized with 1 N HCl, washed with water and dried over
ꢁ
C
(
(
C
55
H41As
2
2 3
O Ru
ꢀ1
ꢀ1
3
.94; N, 2.60. IR (KBr, cm ): 1599 s
n
(C
]
NeN
]
C), 1443 s
O). H NMR (400 MHz, DMSO-d ) (
0.5 (s, 1H, CH]N), 8.5e7.3 (m, 40H, aromatic). C NMR (100 MHz,
DMSO-d ) ( ppm): 203.39 (RueCO), 165.24 (N]CeO), 155.47
CH]N), 153.16, 138.85, 136.33, 134.43, 132.37, 131.13, 130.43,
(AsPh3)
n ,
1
1260 m
n(CeO),1946 s
n
(C
^
6
d
ppm):
2 4
anhydrous Na SO . The combined organic layer passed through
13
1
a short path of silica gel and then subjected to GCeMS analysis. The
conversions obtained are related to the residual unreacted ketone
and are averages of two runs in the case of all catalytic reactions.
6
d
(
1
29.81, 129.04, 128.87, 128.08, 127.25, 126.44, 123.54, 117.36, 112.22.
3
ꢀ1
ꢀ1
UVevis (CH
3
CN,
lmax/nm;
3 /dm mol
cm ): 422(4090),
Acknowledgments
314(10,290), 248(14,880).
We sincerely thank Council of Scientific and Industrial Research
(CSIR), New Delhi for financial support [09/475(0140)
2008eEMReI] and for Senior Research Fellowship to R.N.P. We
express sincere thanks to DSTeFIST, India for the use of Bruker
400 MHz spectrometer and Bruker Smart APEX II diffractometer at
the School of Chemistry, Bharathidasan University, Tiruchirappalli.
4
.3.7. [Ru(L3)(CO)(AsPh
Colour: Yellow brown; Yield: 74 mg, 73%; M.p.: 232e234
with decomposition); Anal. Calc. for BrN
1108.74 g mol ): C, 59.58; H, 3.73; N, 2.53. Found: C, 59.45; H,
3
)
2
] (R ¼ Br; E ¼ As) (7)
ꢁ
C
(
(
3
C
55
H41As
2
2 3
O Ru
ꢀ
1
ꢀ1
.70; N, 2.58. IR (KBr, cm ): 1596 s
n
(C
]
NeN
]
C), 1447 s
n
(AsPh3)
,
)
1
1259 m
n
(CeO), 1949 s
n
(C
^
O)
.
H NMR (400 MHz, DMSO-d
6
1
3
(
(
1
1
d
ppm): 10.5 (s, 1H, CH]N), 8.5e7.2 (m, 40H, aromatic). C NMR
100 MHz, DMSO-d ) ( ppm): 204.23 (RueCO), 167.04 (N]CeO),
56.77 (CH]N), 154.56, 139.45, 136.93, 134.40, 132.73, 131.30,
30.48, 129.85, 129.05, 128.80, 128.11, 127.15, 126.69, 123.29, 117.06,
Appendix A. Supplementary material
6
d
CCDC 881698 contains the supplementary crystallographic data
3
ꢀ1 ꢀ1
112.32. UVevis (CH
3
CN,
l
max/nm; /dm mol cm ): 426(4180),
3
319(10,520), 244(15,310).