S. Selvamurugan et al. / Journal of Organometallic Chemistry 803 (2016) 119e127
121
n
N-H); 1940 (s,
); 1094, 698 (s, for PPh
95, 421, 446. 1H NMR (CDCl
n
C
^^
O
); 1644 (s,
). UVeVis (CH
, 400 MHz, ppm): 11.15 (s, 1H,
n
C
]
O
),1546 (s,
n
C
]
N
); 1373 (m,
n
C-
previously reported (ESIy).
O
3
3
2
Cl ), max (nm): 249, 329,
2
l
3
2.5. X-ray crystallographic study
NHQuinoline); 8.42 (s, 1H, HC]N); 8.25 (s, 1H, Ring CH); 7.92e6.91
m, 39H, Ar H). 13C { H} NMR (CDCl
1
,100 MHz, ppm): 201.36 (C^O),
A crystal of 2 was mounted on a glass fiber and used for data
collection. Crystal data were collected at 296 K using a Gemini A
Ultra Oxford Diffraction automatic diffractometer. Graphite mon-
(
1
3
72.89C]O); 159.94 (CeO); 150.14 (eHC]N); 122.03e135.86 (Ar
31
1
C). P { H} NMR (CDCl
mass(m/z) for C54
3
, 162 MHz, ppm): 41.62 (PPh
3
). Calcd ESI
H
42
N
3
O
3
2
P RuCl is 979.4. Found: 980.9.
ochromated Mo-Ka radiation (
l
¼ 0.71073 Å) was used throughout.
The absorption corrections were performed by multi-scan method.
Corrections were made for Lorentz and polarization effects. The
structure was solved by direct method using the program SHELXS
[30]. Refinement and all further calculations were carried out using
SHELXL. The H atoms were included in calculated positions and
treated as riding atoms using the SHELXL default parameters. The
non-hydrogen atoms were refined anisotropically, using weighted
2
.3.2. [RuCl(CO)(AsPh
-oxo-1,2-dihydroquinoline-3-carbaldehyde benzhydrazide (L
0.291 g, 1 mmol) was reacted with [RuHCl(CO)(AsPh ] (1.084 g,
mmol) to form complex 2. Yield ¼ 0.7898 g (74%). Mp: 278 C.
Anal. Calcd for C54 As RuCl: C, 60.77; H, 3.97; N, 3.94%.
Found: C, 60.62; H, 4.29; N, 3.76%. IR (KBr discs, cm ): 3053 (ms,
3 2 1
) (L )] (2)
2
1
)
(
1
3 3
)
ꢁ
H
42
N
3
O
3
2
ꢀ
1
2
n
N-H); 1948 (s,
); 1077, 693 (s, for AsPh
22, 395, 428. 1H NMR (CDCl3, 400 MHz, ppm): 11.11 (s, 1H,
n
C
O
^^ ); 1651 (s,
n
]
C O
),1546 (s,
n ]
C N
); 1371 (m,
n
C-
full-matrix least squares on F . Atomic scattering factors were
incorporated in the computer programs.
O
3
3
). UVeVis (CH
2
2
Cl ),
lmax (nm): 254, 275,
NHQuinoline); 8.35 (s, 1H, eCH]N); 8.15 (s, 1H, Ring CH); 7.95e6.95
3. Results and discussion
13
1
(
(
m, 39H, Ar H). C { H} NMR (CDCl3, 100 MHz, ppm): 203.12
C^O); 174.03 (C]O); 160.28 (CeO); 153.57 (eHC]N);
3.1. Synthesis and characterization of ruthenium(II) complexes
125.23e139.57 (Ar C). Calcd ESI mass(m/z) for C54
42 3 3 2
H N O As RuCl
is 1067.3. Found: 1068.1.
The 2-oxo-1,2-dihydroquinoline-3-carbaldehyde benzhydrazide
1 2
(L ) and 2-oxo-1,2-dihydroquinoline-3-carbaldehyde isoniazid (L )
2
.3.3. [RuCl(CO)(PPh
-oxo-1,2-dihydroquinoline-3-carbaldehyde
0.292 g, 1 mmol) was reacted with [RuHCl(CO)(PPh
3
)
2
(L
2
)] (3)
ligands were prepared by the reactions of 2-oxo-1,2-
dihydroquinoline-3-carbaldehyde with benzhydrazide/isoniazid
in methanol. The ruthenium(II) complexes were obtained by the
direct reaction of the ligands with ruthenium(II) starting material,
2
isoniazid
2
(L )
(
1
3
)
3
] (0.952 g,
ꢁ
mmol) to form complex 3. Yield ¼ 0.8333 g (85%). Mp: 259 C.
Anal. Calcd for C53
Found: C, 64.77; H, 4.15; N, 5.90%. IR (KBr discs, cm ): 3054 (ms,
H
41
N
4
O
3
P
2
RuCl: C, 64.93; H, 4.22; N, 5.71%.
3 3 3 3
[RuHCl(CO) (PPh ) ] and [RuHCl(CO) (AsPh ) ] in ethanolic medium
ꢀ1
under reflux condition (Scheme 1). The single crystals of new
ruthenium(II) complex 2 were isolated from the solution of column
purified complex by slow evaporation over a period of 15 days. All
the complexes are air stable for extended periods and remarkably
soluble in methanol, ethanol, dichloromethane, chloroform,
acetonitrile, dimethylformamide and dimethylsulfoxide. The
analytical data (C, H, N) of the new complexes (1e4) are in good
agreement with the proposed molecular formulas.
n
N-H); 1949 (s,
n
C
^^
O
); 1656 (s,
). UVeVis (CH
, 400 MHz, ppm): 11.38 (s, 1H, NHQuinoline);
.45 (s, 1H, eCH]N); 8.28 (s, 1H, Ring CH); 7.91e6.82 (m, 38H, Ar
n
C
]
O
),1498 (s,
n
C
]
N
); 1370 (m,
n
C-
O
); 1092, 695 (s, for PPh
3
2
Cl ),
2
lmax (nm): 253, 330,
1
3
8
84, 448. H NMR (CDCl
3
13
1
H). C { H} NMR (CDCl
O); 158.29 (CeO); 148.73 (eHC]N); 120.03e138.86 (Ar C). P { H}
NMR (CDCl , 162 MHz, ppm): 40.69 (PPh ). Calcd ESI mass(m/z) for
RuCl is 980.3. Found: 981.2.
3
, 100 MHz, ppm): 202.86 (C^O); 170.89C]
3
1
1
3
3
53 41 4 3 2
C H N O P
3.2. X-ray crystallography
2
.3.4. [RuCl(CO)AsPh
-oxo-1,2-dihydroquinoline-3-carbaldehyde
0.292 g, 1 mmol) was reacted with [RuHCl(CO)(AsPh
3 2 2
) (L )] (4)
2
isoniazid
(L
2
)
The molecular structure of the complex 2 has been determined
(
1
3
)
3
] (1.084 g,
by single crystal X-ray diffraction to find out the coordination mode
of the hydrazone ligands in the complex. The summary of the data
collected and the refinement parameters were given in Table 1
whereas selected bond lengths and bond angles were given in
Table 2. The ORTEP of the complex 2 has been depicted in Fig. 2. The
ligand is coordinated to ruthenium ion through the azomethine
nitrogen and imidolate oxygen atoms, forming a five-membered
ꢁ
mmol) to form complex 4. Yield ¼ 0.8332 g (78%). Mp: 265 C.
Anal. Calcd for C53
Found: C, 59.38; H, 4.05 N, 5.37%. IR (KBr discs, cm ): 3053 (ms,
); 1927 (s, ); 1658 (s, ), 1503 (s, ); 1370 (m,
077, 693 (s, for AsPh ). UVeVis (CH Cl ), max (nm): 255, 271, 390,
400 MHz, ppm): 10.95 (s, 1H, NHQuinoline); 8.46
41 4 3 2
H N O As RuCl: C, 59.59; H, 3.87; N, 5.24%.
ꢀ
1
n
N-
C-O);
H
1
4
n
^
C O
n ]
C O
n ]
C N
n
3
2
2
l
1
67. H NMR (CDCl
3
13
ꢁ
(
{
s, 1H, eCH]N); 8.19 (s, 1H, Ring CH); 7.89e6.20 (m, 38H, Ar H).
C
chelate ring with a bite angle O(2)ꢀRu(2)ꢀN(1) of 76.37(13) . The
1
H} NMR (CDCl
3
, 100 MHz, ppm): 204.01 (C^O); 171.69 C]O);
Ru(2)ꢀN(1) bond distance is 2.114(4) Å, and the Ru(2)ꢀO(2) dis-
tance is 2.4840(3) Å. The other four sites are occupied by arsine
atoms of two triphenylarsine ligands which are mutually trans to
each other with Ru(2)ꢀAs(1) and Ru(2)ꢀAs(2) distances of
2.4706(8) and 2.4632(8) Å respectively. A chloride and a carbonyl
group are also bound to ruthenium with Ru(2)ꢀCl(1) and Ru(2)ꢀ
C(1) distances of 2.4019(13) and 1.847(5) Å respectively. The
observed bond distances are comparable with those found in other
1
62.73 (CeO); 148.84 (eHC]N); 125.52e137.87 (Ar C). Calcd ESI
41 4 3 2
mass(m/z) for C53H N O As RuCl is 1068.2. Found: 1069.1.
2.4. Typical procedure for amidation of amines with alcohols
In a 25 mL round bottomed flask were placed 0.25 mol% of
ruthenium(II) catalyst, 1 mmol of alcohol, 1 mmol of amine, 20 mol
%
of sodium hydride (NaH), 5 mol% CH
3
CN and 2.0 mL of toluene.
reported ruthenium complexes containing AsPh
3
[31]. The cis an-
ꢁ
ꢁ
The reaction flask was heated at 120 C for 12 h under argon at-
mosphere. Upon completion of the reaction (reaction was moni-
tored by TLC), the solvent was removed under vacuum and the
resulting residue was purified by column chromatography on silica
gel using ethylacetate/n-hexane solvent mixture. The amide prod-
uct was dried under vacuum overnight. The resulting amides were
gles O(2)ꢀRu(2)ꢀAs(1)
¼
89.82(9)
and C(1)ꢀRu(2)ꢀ
ꢁ
As(1) ¼ 88.74(16) are acute, whereas the other cis angles Cl(1)ꢀ
ꢁ
ꢁ
Ru(2)ꢀAs(1) ¼ 91.47(4) , N(1)ꢀRu(2)ꢀAs(1) ¼ 90.54(12) , N(1)ꢀ
ꢁ
ꢁ
Ru(2)ꢀCl(1) ¼ 92.69(10) , C(1)ꢀRu(2)ꢀCl(1) ¼ 96.67(15) and
ꢁ
C(1)ꢀRu(2)ꢀO(2) ¼ 94.28(17) are obtuse. The trans angles As(2)ꢀ
ꢁ
Ru(2)ꢀN(1) ¼ 177.61(2), O(2)ꢀRu(2)ꢀCl(1) ¼ 169.0(9) and C(1)ꢀ
1
13
ꢁ
identified by comparison of the H and C NMR data with those
Ru(2)ꢀN(1) ¼ 170.63(17) deviate from linearity. The variations in