Photochemical reactions of metal carbonyls [M(CO)6(M = Cr, Mo, W), Mn(CO)3Cp] with 3[4-ethyl(phenyl)imino][1H-indol-2-one] and 3[4-butyl(phenyl)imino][1H-indol-2-one]

Article abstract of DOI:10.14233/ajchem.2017.20004

Four new complexes of M(CO)₅(ISE) [M = Mo (1), Cr (2), W (3)] and Mn(CO)₃(ISE) (4), where ISE is 3[4-ethyl(phenyl)imino][1H-indol-2-one] has been synthesized by the photochemical reactions of metal carbonyls M(CO)₆(M = Mo, Cr, W) and Mn(CO)₃C_p with ISE (1-4). Four new complexes of M(CO)₅(ISB) [M = Mo (5), Cr (6), W (7)] and Mn(CO)₃(ISB) (8), where ISB is 3[4-butyl(phenyl)imino][1H-indol-2-one] has been synthesized by photochemical reactions of metal carbonyls M(CO)₆(M = Mo, Cr, W) and Mn(CO)₃ C_p with ISB (5-8). The complexes have been characterized by elemental analysis, FT-IR, ¹H and ¹³C NMR spectroscopy. The spectroscopic studies show that, 3[4-ethyl(phenyl)imino][1H-indol-2-one] and 3[4-butyl(phenyl)imino][1H-indol-2-one] ligands, behave as a monodentate ligand and coordinate via C=N donor atom to the central metal atom in M(CO)₅(ISE) (1-3) and M(CO)₅(ISB) (5-7) where M = Mo, Cr, W and as a tridentate ligand coordinating via imine nitrogen donor atom (C=N), oxygen donor atom (C=O) and ring NH donor atom in Mn(CO)₃(ISE) (4) and Mn(CO)₃(ISB) (8).

Full text of DOI:10.14233/ajchem.2017.20004

Asian Journal of Chemistry; Vol. 29, No. 2 (2017), 235-238
A
SIAN
J
OURNAL OF HEMISTRY
C
http://dx.doi.org/10.14233/ajchem.2017.20004
Photochemical Reactions of Metal Carbonyls [M(CO)
6
3 p
(M = Cr, Mo, W), Mn(CO) C ] with
3[4-Ethyl(phenyl)imino][1H-indol-2-one] and 3[4-Butyl(phenyl)imino][1H-indol-2-one]
1,*
2
S. SENER and A. ERCAG
1
2
Ege University, Community College of Aliaga, TR-35100, Izmir, Turkey
Chemistry Department, Enginee ring Faculty, Istanbul University, 34850, Istanbul, Turkey
*
Corresponding author: E-mail: sevil.sesener@gmail.com
Received: 31 March 2016;
Accepted: 30 September 2016;
Published online: 30 November 2016;
AJC-18136
Four new complexes of M(CO)
5
(ISE) [M = Mo (1), Cr (2), W (3)] and Mn(CO)
3
(ISE) (4), where ISE is 3[4-ethyl(phenyl)imino][1H-
(M = Mo, Cr, W) and Mn(CO) with ISE
(ISB) (8), where ISB is 3[4-butyl(phenyl)imino][1H-
indol-2-one] has been synthesized by photochemical reactions of metal carbonyls M(CO) (M = Mo, Cr, W) and Mn(CO) with ISB
5-8). The complexes have been characterized by elemental analysis, FT-IR, H and C NMR spectroscopy. The spectroscopic studies
show that, 3[4-ethyl(phenyl)imino][1H-indol-2-one] and 3[4-butyl(phenyl)imino][1H-indol-2-one] ligands, behave as a monodentate
ligand and coordinate via C=N donor atom to the central metal atom in M(CO) (ISE) (1-3) and M(CO) (ISB) (5-7) where M = Mo, Cr, W
and as a tridentate ligand coordinating via imine nitrogen donor atom (C=N), oxygen donor atom (C=O) and ring NH donor atom in
Mn(CO) (ISE) (4) and Mn(CO) (ISB) (8).
indol-2-one] has been synthesized by the photochemical reactions of metal carbonyls M(CO)
1-4). Four new complexes of M(CO) (ISB) [M = Mo (5), Cr (6), W (7)] and Mn(CO)
6
3
C
p
(
5
3
6
3
C
p
1
13
(
5
5
3
3
Keywords: Isatin, 1,2,4-Triazole, Schiff base, Metal carbonyl, Photochemical reaction.
(
7)] and Mn(CO)
3
(ISB) (8), where ISB is 3[4-butyl(phenyl)-
INTRODUCTION
imino][1H-indol-2-one] hve been described. The complexes
The synthetic versality of isatin (1H-indol-2,3-dione) has
1
13
are characterized by elemental analysis, FT-IR, H and
NMR spectroscopy. ISE coordinates to the metal via imine
nitrogen donor atom in M(CO) (ISE) (1-3) (Scheme-I) and
via imine nitrogen, ring CO oxgen donor atom and ring NH
nitrogen donor atoms in [Mn(CO) (ISE)]; (4) (Scheme-II).
ISB coordinates to the metal via imine nitrogen donor atom in
M(CO) (ISB) (5-7) (Scheme-I) and via imine nitrogen, ring
CO oxygen donor atom and ring NH nitrogen donor atom in
Mn(CO) (ISB)] (4) (Scheme-II).
C
led to extensive use in organic synthesis. It has stemmed from
the interest in the biological and pharmacological properties
of the derivatives [1,2]. Isatin and derivatives of isatin have
been used as reagent in dye industry as well. Although, it was
firstly synthesized for nearly hundred years ago, recently it
was discovered in mamalian tissues and in body fluid. It was
observed that monoamine oxidase was inhibited by isatin and
derivatives in vitro studies [3]. The Schiff bases are an impor-
tant class of ligands in the coordination chemistry [4-6]. Schiff
bases of isatin were reported to posses antibacterial [7-9],
antifungal [10-12], antiviral [13-15], anti-HIV [16-18], anti-
protozoal [19,20] and antihelminthic [21,22] activities.
Our interest in this category of ligands is justified by their
already proved medical and biological implications [23-25].
In the previous studies, metal complexes of 3[4-ethyl(phenyl)-
imino][1H-indol-2-one] (ISE) and 3[4-butyl(phenyl)imino][1H-
indol-2-one] (ISB) were not synthesized by metal salts. In this
paper, a novel photochemical route to form four new complexes;
5
3
5
[
3
EXPERIMENTAL
Reactions were carried out under dry nitrogen using Schlenk
techniques. All solvents were dried and degassed prior to use.
Elemental analyses were carried out using a LECOCHNS-O-
9320 by Technical and Scientific Research Council of Turkey,
TUBITAK. MicromassVG Platform-II LC-MS were recorded
at TUBITAK as well. IR spectra were recordedon samples with
KBr at the Ege University on a Mattson 1000 FT spectrophoto-
meter. HNMR spectra were recorded in DMSO on a 400 MHz
High Performance DigitalFT NMR at TUBITAK. UV irradia-
tions were performed with a medium-pressure 400 W mercury
1
M(CO)
4) where ISE is 3[4-ethyl(phenyl)imino][1H-indol-2-one] and
four new complexes of M(CO) (ISB) [M = Mo (5), Cr (6), W
5
(ISE) [M = Mo(1), Cr (2), W (3) and [Mn(CO)
3
(ISE)]
(
5

236 Sener et al.
Asian J. Chem.
CO
M
–1
Spectral data of ISB: IR (KBr, νmax, cm ): 2978, 2953,
R
OC
OC
CO
CO
R
2927, 2365 (b, NH ring), no observed CO), 1753 (CO ring),
CO
OC
N
O
CO
CO
1650 (C=N-C), 1523, 1472 (T -ring), 1375, 1344, 1260, 1217
hv
1
M
+
N
OC
(
T
2
-ring), 1184, 1012 (T
3
-ring), 930 (T -ring), 815 (benzene).
4
CO
N
H
1
H NMR (δ, DMSO-d ): 10.85 (NH), 7.0, 7.35 (CH)benzene),
6.65 (CH indol), 4.05 (CH, CH
ppm. C NMR (δ, DMSO-d
C), 156.8 (CO-ring), 34.31 (CH, CH alkyl), 13.78 (CH, CH
6
N
O
H
M: Mo, Cr, W
R: C H ; ISE
2 5
2
alkyl), 1.28(CH, CH
3
alkyl)
M: Mo, R: C H ; ISE; Mo(ISE)(CO)
(
)
1
)
)
R: C H ; ISB
2
5
5
13
4
9
M: Cr, R: C H ; ISE; Cr(ISE)(CO) (2
6
): no observed (CO), 165.2 (C=N-
2
5
5
M: W, R: C H ; ISE; W(ISE)(CO)
(
3
)
(
2
5
5
2
3
M: Mo, R: C H ; ISB; Mo(ISB)(CO)
5
4
9
5
alkyl) ppm.
M: Cr, R: C H ; ISB; Cr(ISB)(CO) (6)
5
4
9
M: W, R: C H ; ISB; W(ISB)(CO) (7
)
Synthesis of metal carbonyl complexes: Reactions were
carried out under nitrogen using Schlenk techniques. All
solvents were dried and degassed prior to use.The complexes,
4
9
5
Scheme-I: Photochemical reaction of metal carbonyl and ISE and ISB
R
R
M(CO)
5
(ISE) (1-3) [M = Mo, Cr, W] and Mn(CO)
3
(ISE) (4)
N
[
ISE:3[4-ethyl(phenyl)imino][1H-indol-2-one] and
N
hV
M(CO)
5
(ISB) (5-7) [M = Mo, Cr, W] and, Mn(CO)
3
(ISB) (8)
+
N
O
Mn
CO
N
H
O
CO
CO
[ISB: 3[4-butyl(phenyl)imino][1H-indol-2-one] were prepared
by the photochemical reactions of metal carbonyls and
Mn(CO)
OC
CO
Mn
OC
MnC (CO)3
R: C H ; ISE
2 5
R: C H ; ISB
p
R: C H ; ISE; Mn(CO) (ISE) (
R: C H ; ISB; Mn(CO) (ISB) (
4
8
)
)
3
C with ISE and ISB, respctively in 70-80 % yields.
p
2
5
3
4
9
4
9
3
Synthesis of Mo(ISE)(CO) (1): Mo(CO) (1 mmol) and
5
6
P 3
Scheme-II: Photochemical reaction of MnC (CO) with ISE and ISB
ISE (1 mmol) were dissolved in tetrahydrofuran (80 mL). The
solution was irradated for 1 h using a 400 W medium pressure
mercury lamp through a quarz-walled immersion well reactor
while stirring at -78 °C in ice-acetone mixture. During irradia-
tion, the colour of the solution changed from colourless to
yellow. After irradiation, the reaction mixture was evaporated
under vacuum, yielding a light yellow solid. The solid was
then filtered, washed with alcohol and hexane and dried under
vacuum [27].Yield: (72 %). m.p.: 245 °C. Found (%): C, 51.45,
H, 3.14, N, 2.97. Anal. calcd. for (%): C, 53.4, H, 2.99, N,
lamp through a quartz-walled immersion well reactor. Melting
points were determined on Boetius heating-plate microscope.
Synthesis of 3[4-ethyl(phenyl)imino][1H-indol-2]-one
(ISE): For the preaparation of ISE, a solution of isatin (1 mmol)
in ethanol (25 mL) was added to a magnetically stirred solution
of ethylaniline (1 mmol) in ethanol (25 mL). The mixture was
refluxed for 4 h on water bath. The orange precipitated products
formed during reflux was cooled at room temperature. It was
filtered, washed with ethanol and dried over P
2
O in vacuum.
5
2
.87.
Spectral data of Mo(ISE)(CO)
969 (b, NH ring), 2076 (s, CO), 1976 (s, CO), 1876 (s, CO),
The products thus obtaned was recrystallized from methanol
to give ISE ligand (Scheme-III) [26].
–1
5
: IR (KBr, νmax, cm ):
2
R
1723 (CO ring), no observed (C=N-C), 1507, 1469 (T -ring),
1
1
7
353, 1269, 1207 (T
53 (benzene). H NMR (δ, DMSO-d
2
-ring), 1115 T
3
-ring), 976 (T
): 12.3 (NH), 7.3, 7.9
alkyl),
): 205.23,
198.68, 185.66 (CO), 169.7 (C=N-C), 164.7 (CO-ring), 29.42
CH, CH alkyl), 17.2 (CH, CH alkyl) ppm.
Synthesis of Cr(ISE)(CO) (2): A similar synthetic
procedure as that used for 1a was used except that Mo(CO)
was replaced by Cr(CO) , giving pale-yellow crystals. Yield:
76 %).m.p.: 252 °C. Found (%): C, 60.0, H, 3.00, N, 2.96.
Anal. calcd. for (%): C, 58.9, H, 3.29, N, 3.32.
Spectral data of Cr(ISE)(CO) : IR (KBr, νmax, cm ):
969 (b, NH ring), 2061 (s, CO), 1930 (s, CO), 1723 (CO
ring), 1576 (m, C=N-C), 1500, 1453(T -ring), 1376, 1269, 1207
-ring), 1092, 1038 (T -ring), 930 (T -ring), 815 (benzene).
H NMR (δ, DMSO-d ): 12.7 (NH), 7.0, 7.55 ((CH)benzene),
.45, 6.53 (CH indol), 2.65, 2.4 (CH, CH alkyl), 1.48 (CH,
): 222.70, 201.40,
4
-ring), 838,
O
N
1
6
+
H
2
N
R
(CH)benzene), 6.1, 6.3 (CH indol), 2.73, 2.67(CH, CH
2
N
H
O
N
H
O
13
1.35(CH, CH
3
alkyl) ppm. C NMR (δ, DMSO-d
6
Isatin
R: C H5
→
→
ethylaniline
butylaniline
R: C H5
→
→
ISE ligand
ISB ligand
2
2
R: C H9
R: C H9
4
4
(
2
3
Scheme-III: Synthesis reaction of ISE and ISB ligand
5
–1
6
Spectral data of ISE: IR (KBr, νmax, cm ): 2978, 2953,
927, 2365 (b, NH ring), no observed (CO), 1753 (CO ring),
6
2
1
(
650 (m, C=N-C), 1523, 1472 (T
217 (T -ring), 1184, 1012 (T -ring), 930 (T
H NMR (δ, DMSO-d ): 11.9 (NH), 7.0, 7.40 ((CH)benzene),
.43, 6.65 (CH indol), 2.50 (CH, CH alkyl), 1.23(CH, CH
): no observed (CO), 163.58
C=N-C), 154.65 (CO-ring), 27.63 (CH, CH alkyl), 15.57 (CH,
CH alkyl) ppm.
Synthesis of 3[4-butyl(phenyl)imino][1H-indol-2-one]
ISB): For the preaparation of 2, a solution of isatin (1 mmol)
1
-ring), 1375, 1344, 1260,
1
2
3
4
-ring), 815 (benzene).
–1
1
5
6
2
6
2
3
13
1
alkyl) ppm. C NMR (δ, DMSO-d
6
(
T
2
3
4
(
2
1
6
3
6
CH
2
1
3
3
alkyl) ppm. C NMR (δ, DMSO-d
6
(
1
95.80 (CO), 173.50 (C=N-C), 161.30 (CO-ring), 32.61 (CH,
CH alkyl), 16.50 (CH, CH alkyl) ppm.
Synthesis of W(ISE)(CO) (3): A similar synthetic
procedure as that used for 1a was used except that Mo(CO)
was replaced by W(CO) , giving pale-yellow crystals. Yield:
81 %). m.p.: 250 °C. Found (%): C, 47.14, H, 3.20, N, 3.27.
Anal. calcd. for (%): C, 45.03, H, 2.52, N, 2.37.
in ethanol (25 mL) was added to a magnetically stirred solution
of butyl aniline (1 mmol) in ethanol (25 mL). The mixture
was refluxed for 4 h on water bath. The orange precipitated
products formed during reflux was cooled room temperature.
It was filtered, washed with ethanol and dried over P
vacuum. The products thus obtaned was recrystallized from
2
3
5
6
6
2
O in
5
(
methanol to give ISB ligand (Scheme-III) [26].

Vol. 29, No. 2 (2017)
Photochemical Reactions of Metal Carbonyls 237
–
1
Spectral data of W(ISE)(CO)
5
: IR (KBr, νmax, cm ):
CO), 1723 (CO ring), 1592 (C=N-C), 1523, 1461 (T
1376, 1323, 1284, 1207 (T -ring), 1100, 1061, 1023 (T
915 (T
): 12.1 (NH), 7.20, 7.51 (CH)benzene), 6.00, 6.53 (CH indol),
1
-ring),
2
969 (b, NH ring), 2069 (s, CO), 1976, 1923 (s, CO), 1807 (s,
CO), 1715 (CO ring), no observed (C=N-C), 1515, 1469 (T
ring), 1330, 1261, 1200 (T -ring), 1100, 1030 (T -ring), 976
): 12.1 (NH),
.0, 7.45 (CH)benzene, 1H, m), 6.21, 6.8 (CH indol), 2.50,
2
3
-ring),
1
1
-
4
-ring), 884, 815, 746 (benzene). H NMR (δ, DMSO-
2
3
d
6
1
13
(
T
4
-ring), 815 (benzene). H NMR (δ, DMSO-d
6
4.4 (CH, CH
2
alkyl), 1.48 (CH, CH
3
alkyl) ppm. C NMR (δ,
7
2
DMSO-d ): 219.15, 198.58, 185.56 (CO), 168.76 (C=N-C),
6
13
.40 (CH, CH
): 203.60, 201.30, 195.80 (CO), 175.60 (C=N-C),
60.2 (CO-ring), 30.78 (CH, CH alkyl), 16.3 (CH, CH alkyl)
ppm.
Synthesis of Mn(ISE)(CO)
2
alkyl), 1.54 (CH, CH
3
alkyl) ppm. C NMR (δ,
162.12 (CO-ring), 35.40 (CH, CH
alkyl) ppm.
2
alkyl), 13.50 (CH, CH
3
DMSO-d
6
1
2
3
Synthesis ofW(ISB)(CO)
dure as that used for 1a was used except that Mo(CO)
replaced by W(CO) , giving pale-yellow crystals. Yield: (85
5
(7): A similar synthetic proce-
6
was
3
(4): MnC
p
(CO)
3
(1 mmol)
6
and ISE (1 mmol) were dissolved in tetrahydrofuran (80 mL).
The solution was irradated for 1 h using a 400 W medium
pressure mercury lamp through a quarz-walled immersion well
reactor while stirring at -78 °C in ice-acetone mixture. During
irradiation, the colour of the solution changed from colourless
to yellow. After irradiation, the reaction mixture was evapo-
rated under vacuum [27], yielding a light yellow solid. The
solid was then filtered, washed with alcohol and hexane and
dried under vacuum.Yield: (69 %). m.p.: 267 °C. Found (%):
C, 60.90, H, 3.50, N, 3.75. Anal. calcd. for (%): C, 62.32, H,
%). m.p.: 261 °C. Found (%): C, 45.47, H, 3.06, N, 2.44.Anal.
calcd. for (%): C, 46.02, H, 2.81, N, 2.27.
–1
Spectral data of W(ISB)(CO)
2938 (b, NH ring), 1953 (s, CO), 1723 (CO ring), no observed
(C=N-C), 1523, 1476 (T -ring), 1323, 1276 (T -ring), 1192,
1123, 1038 (T -ring), 938 (T -ring), 884, 815, 746 (benzene).
H NMR (δ, DMSO-d ): 10.76 (NH), 7.0, 7.45 (CH)benzene),
6.20, 6.80 (CH indol), 4.45(CH, CH alkyl), 1.54(CH, CH
): 206.19, 201.78, 194.56,
190.48, 185.06 (CO), 175.03 (C=N-C), 159.46 (CO-ring),
30.59 (CH, CH alkyl), 12.06 (CH, CH alkyl) ppm.
Synthesis of Mn(ISB)(CO) (8): MnC (CO)
5
: IR (KBr, νmax, cm ):
1
2
3
4
1
6
2
3
13
alkyl) ppm. C NMR (δ, DMSO-d
6
3
.47, N, 3.9.
Spectral data of Mn(ISE)(CO)
010 (s, CO), 1930 (s, CO), 1650 (CO ring), 1580 (m, C=N-
-ring), 1366, 1255 (T -ring), 1100, 1010
2
3
–1
3
: IR (KBr, νmax, cm ):
3
p
3
(1 mmol)
2
and ISB (1 mmol) were dissolved in tetrahydrofuran (80 mL).
The solution was irradated for 1 h using a 400 W medium
pressure mercury lamp through a quarz-walled immersion well
reactor while stirring at -78 °C in ice-acetone mixture. During
irradiation, the colour of the solution changed from colourless
to yellow. After irradiation, the reaction mixture was evapo-
rated under vacuum, yielding a light yellow solid. The solid
was then filtered, washed with alcohol and hexane and dried
under vacuum [27]. Yield: (77 %). m.p.: 272 °C. Found (%):
C, 61.85, H, 3.38, N, 3.62. Anal. calcd. for (%): C, 62.31, H,
3.40, N, 3.74.
C), 1505, 1771 (T
-ring), 987 (T -ring), 810 (benzene). H NMR (δ, DMSO-
): 7.20, 7.60 ((CH)benzene), 6.55 (CH indol), 2.70 (CH,
1
2
1
(
T
3
4
d
6
13
CH
): 82.45, 81.65 (CO), 171.43 (C=N-C), 160.19 (CO-ring),
no observed (C ) ppm.
Synthesis of Mo(ISB)(CO)
2
alkyl), 1.34 (CH, CH
3
alkyl) ppm. C NMR (δ, DMSO-
d
6
p
5
(5): Mo(CO) (1 mmol) and
6
ISB (1 mmol) were dissolved in tetrahydrofuran (80 mL). The
solution was irradated for 1 h using a 400 W medium pressure
mercury lamp through a quarz-walled immersion well reactor
while stirring at -78 °C in ice-acetone mixture. During irra-
diation, the colour of the solution changed from colourless to
yellow. After irradiation, the reaction mixture was evaporated
under vacuum, yielding a light yellow solid. The solid was
then filtered, washed with alcohol and hexane and dried under
vacuum [27].Yield: (67 %). m.p.: 243 °C. Found (%): C, 56.28,
H, 3.96, N, 2.88.Anal. calcd. for (%): C, 54.34, H, 3.32, N,
–1
Spectral data of Mn(ISB)(CO)
2012 (s, CO), 1932 (br, CO), 1624 (CO ring), 1579 (C=N-C),
1532, 1777 (T -ring), 1315, 1260(T -ring), 1112, 1002 (T
ring), 933 (T -ring), 820 (benzene). H NMR (δ, DMSO-d
6.90, 7.40 ((CH)benzene), 6.90(CH indol, 1H, m), 3.90 (CH,
3
: IR (KBr, νmax, cm ):
1
2
1
3
-
):
4
6
13
CH
NMR (δ, DMSO-d
165.32 (CO-ring), no observed (C
2
alkyl), 1.25(CH, CH
): 83.55, 82.95 (CO), 177.56 (C=N-C),
) ppm.
3
alkyl), no observed (C ) ppm. C
p
6
2
.18.
Spectral data of Mo(ISB)(CO)
938, 2346 (b, NH ring), 2069 (s, CO), 1892 (s, CO), 1715
-ring), 1361,
-ring), 969 (T -ring), 846,
53 (benzene). H NMR (δ, DMSO-d ): 11.79 (NH), 7.50,
.00 (CH)benzene), 5.80, 6.70 (CH indol), 4.20(CH, CH
p
–1
5
: IR (KBr, νmax, cm ):
RESULTS AND DISCUSSION
2
(
CO ring), no observed (C=N-C), 1507, 1469 (T
1
The assignments of FTIR bands were made taking into
consideration literature data for compounds containing
appropriate structural fragments. There are four medium
1284, 1207 (T
2
-ring), 1100, 1023 (T
3
4
1
7
8
6
-
1
2
intensity bands around 2978, 2953, 2927 and 2365 cm in the
spectrum of the ligand due to the interaction between ν(N-H)
[28]. This fact is further supported by the apperance of a band
1
3
alkyl), 1.35(CH, CH
3
alkyl) ppm. C NMR (δ, DMSO-d
6
):
2
02.13, 196.58, 181.56 (CO), 170.09 (C=N-C), 168.05 (CO-
ring), 37.72 (CH, CH alkyl), 14.78 (CH, CH alkyl) ppm.
Synthesis of Cr(ISB)(CO) (6): A similar synthetic proce-
dure as that used for 1a was used except that Mo(CO) was
replaced by Cr(CO) , giving pale-yellow crystals. Yield:
71 %). m.p.: 258 °C. Found (%): C, 57.91, H, 4.16, N, 3.17.
Anal. calcd. for (%): C, 59.73, H, 3.65, N, 3.35.
Spectral data of Cr(ISB)(CO) : IR (KBr, νmax, cm ):
953, 2930 (b, NH ring), 2061 (s, CO), 1984, 1930, 1884 (br,
-
1
2
3
around 1753 cm assignable to ν(C=O) [28]. A broad band
-1
5
around 1650 cm can be assigned to ν(C=N) vibration mode
[28]. The ligand molecule contains a thioamide group, H-C=O
and gives rise to four characteristic bands in the IR spectra.
The thioamide band has major and minor contributions from
ν(N-H) and ν(C=N), respectively and is observed at around
6
6
(
–1
-1
5
1525-1470 cm in the IR spectra. Due to the minor contribution
2
from ν(C=N), the shift toward a higher wave number is not

238 Sener et al.
Asian J. Chem.
significant and the overall effect is a shift toward the lower
wave number. The thioamide band II has a major contribution
M(CO)
5
(ISB) and Mn(CO)
3
(ISE), Mn(CO)
3
(ISB)were pre-
pared by the photochemical reaction of between M(CO)
Mn(CO) with ISE and ISB. The spectroscopic studies show
that, ISE and ISB behave as a monodentate ligands coordi-
nating via nitrogen [Ar-C=N-Ar exocyclic] donor atom in
the complexes, M(CO)
behaves as tridentate ligand coordinating via Ar-C=N-Ar
exocyclic, C=O endocyclic and ring N donor atoms in the
complex Mn(CO)
6
,
-1
from ν(C=N) and is observed around 1375-1217 cm . The
thioamide band III has a major contribition from ν(C=N) and
minor contribution from ν(C=O) in the spectral region of 1184-
C
3 p
-
1
1
012 cm . The thioamide band IV seems to have a contribution
5
(ISE) (1-3); M(CO) (ISB) (5-7). ISE
5
-1
only from ν(C=O) around 930 cm [28].
The ligand molecule also displays a band around 1650
-1
-1
cm due to ν(C=N) band which shifts to around 1576 cm in
the complex indicating that the nitrogen atom is involved in
the coordination to the metal. Also, the four characteristic
thioamide bands in the spectra of the ligand molecule change
upon complexation. Due to the tautomerism of the thioamide
moiety and the redistrubition of the electron cloud as a result
of complex formation, there is a systematic shift in these bands
in the IR spectra of the complex in comparison to that of the
ligand [28]. These shifts are consistent with the ability of the
imine atom to coordinate to the metal [28].
3
(ISE) (4) and Mn(CO) (ISB)(8).
3
ACKNOWLEDGEMENTS
The authors are grateful to this research was supported
by Ege University Research Found under Project No. 2014/
BMYO/001 and 2013/BMYO/002.
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