Half-sandwich arene ruthenium, rhodium and iridium thiosemicarbazone complexes: synthesis, characterization and biological evaluation

Article abstract of DOI:10.1007/s12039-019-1731-5

Abstract: A series of ruthenium, rhodium and iridium complexes with 4-phenyl-1-(pyridin-4yl)methylene thiosemicarbazide (L1) and 4-phenyl-1-(pyridin-4yl)ethylidene thiosemicarbazide (L2) ligands were synthesized and isolated with hexafluorophosphate as a counter ion. All these complexes were fully characterized with the help of FT-IR, UV-Vis, ¹H NMR, ¹³C NMR and elemental analysis. An agar-well diffusion method was employed for evaluation of antibacterial activities against one Gram-positive bacteria Staphylococcus aureus and two Gram-negative bacteria Escherichia coli, Klebsiella pneumoniae. Antimicrobial activity evaluation revealed that Cp* rhodium complexes has a significant antibacterial activity for all the three strains, Cp* iridium and p-cymene ruthenium complexes have shown moderated activity against the microorganisms but none of the complexes surpass the activity of their reference drugs. Results indicated that all the complexes reported here inhibit the growth of bacteria. Graphic Abstract: Synopsis. A series of ruthenium, rhodium and iridium complexes bearing thiosemicarbazide ligands were synthesized and isolated with hexafluorophosphate as counter ion. Antibacterial potencies of the compounds was reported against Staphylococcus aureus, Escherichia coli, and Klebsiella pneumonia and results shows that all the complexes reported here inhibit the growth of bacteria.[Figure not available: see fulltext.]

Full text of DOI:10.1007/s12039-019-1731-5

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1. Introduction
r u t h en i u m - b a s ed d r u g s m ai n l y b e c au s e o f t h ei r w at er
s o l u b i l i t y w h i ch a l l o w s h a l f - s a n d w ic h c o m p l e x e s t o b e
e as i l y t a i l o r e d f o r c at al y t i c o r b i o l o g i c al a p p l i c a t i o n s .
T h e i n t e r es t i n g c h e mi ca l p r o p er t i es e x h i b i t ed b y t h e
c o m p l e x e s o f r h o d i u m m et al e n c o u r a g e t h e l a r g e
F o r m a n y y e a r s , n e w d r u gs o f a n i n t e r e s ti n g s t ru ct u r e,
u n k n o w n m ol e c u l a r t a r g e t, l ow t o x i c i ty a n d a h i g h
t h e r ap eu ti c i n d ex h a v e b e e n l oo k e d f o r . T h i s i s d u e t o
t h e i m p o s s i b i li t y o f t re a t i n g m a ny s e ri o u s d i s e as es ,
s u c h a s b a c t e r i a l i nf e c ti o n s o r c a nc e r . T h e r u t h en i u m
a r e n e - b a s ed d r u g s h a v e a t t r a c t e d p a r ti c u l a r i nt e re s t i n
6
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7
c o n s i d e r ab l e c u r r en t a t t e n t i o n o f r h o d i u m c h e m i s t r y .
T h e a n t i ca n c e r a ct i v i t y o f i r i d i u m c o m p l e x e s h a v e
m ad e g r e at p r o g re s s , w h e r e a n u m b e r o f i r i d i u m
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c o m p l e x e s s h o w h i g h a n t i ca n c e r e f fe c t . B ut t h e r e
a re r e l a t i v el y f e w r e p o r t s o n t h e a n t i mi cr o b i a l p r o p -
r e c e n t y e a r s . B e s i de p la ti n u m c o m p o u nd s , p i an o -
s t o o l r u t h en i u m h a l f -s a n dw ic h c o m p le x e s a r e t h e v e r y
p r o m i s i n g c l a s s o f a n t im ic ro bia l a n d a n t it u m o r a g e n t s
a s t h e s t e r e oc h e m i s t r y o f t he s e c o m p le x e s o f f e rs a
g o o d p l a t f o r m f or p r o du c i n g n e w m o l e c u l e s b y
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a cc e s s i b le o x i d at i o n s t a te s o f r u t he ni u m ( II a n d I I I) a re
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Electronic supplementary material: The online version of this article (https://doi.org/10.1007/s12039-019-1731-5) contains
supplementary material, which is available to authorized users.

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m
7
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5
1
,
1
3
7
.
1
2
,
1
3
3
.
7
3
2 . 5 c [Cp*RhL1Cl]PF6 [3]:
m -1
0 m( N - H ), 7 m( C = N )
Y
i
e
l
d
:
7
9
%
;
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R
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1
6
6
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8
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7 m( P -F ) ,
7
5
6
;
H
( C =S )
A
c
e
t
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n
i
t
r
i
le
m
a
x
N
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l
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7
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= 8 H z )
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l
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h
P
;
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:
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1
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9
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4
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3
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8
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2
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%
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7
N
M
,
R
(
1
0
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H
z
,
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D
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l
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p
p
m
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1
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8
7
1
2
3
.
7
7
,
.
0
2
2 . 5 h [Cp*IrL2Cl]PF6 [8]:
m -1
8 m( N - H ) , 1 m( C = N )
Y
i
e
l
d
:
7
3
%
;
I
R
(
K
B
1
r
,
-
4
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1
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3
,
8
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3
6
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i
{
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c
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n
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t
r
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l
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, km a x
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n
m
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e
/
1
0
M
c
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4
4
1
6
2
,
8
4
6 m( P - F ) ,
7
5
7
;
H
m -1
)
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h
PF ( 6
6
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4
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9
3
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4
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0
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7
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z
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7
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2
4
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z
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6
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6
8
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t
,
3
H
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D
8
.
3
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o
u
n
d
:
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,
4
0
.
9
1
;
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,
4
.
0
6
;
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8
.
3
8
%
1
3
6
.
3
1
(
s
,
3
H
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,
1
.
6
2
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s
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1
5
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N
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R
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H
z
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O
-
d
p
2
m
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3
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.
3
0
,
1
3
1
.
9
2
,
1
2
9
.
2
8
2 . 5 d [Cp*IrL1Cl]PF6 [4]:
m -1
8 m( N - H ), 3 m( C = N )
Y
i
e
l
d
:
6
7
%
;
I
R
(
K
B
r
,
8
.
9
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7
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8
8
;
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/
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4
-
1
9
m
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P
-
F
)
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(
C
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n
i
t
r
i
l
e
,
k
,
n
m
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e
/
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0
M
c
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c
)
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4
4
1
6
3
,
8
4
6
8
6
;
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s
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x
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9
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9
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0
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z
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7
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8
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M
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.
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l
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r
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H
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r
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6
4
6
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H
A
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4
1
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3
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2
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=
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z
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6
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9
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d
,
(
7
7
. 8 2 ; N , 7 . 3 1 % .
8
.
2
1
)
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,
3
7
.
0
4
;
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,
3
.
7
6
;
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2
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n
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3
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2
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=
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1
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1
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1
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2 6 9 .9 7
V
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i
s
3
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4
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1
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e
t
o
n
i
t
r
i
l
e
,
k
,
n
m
(
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/
1
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m
a
x
(
6
.
0
3
7
)
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3
5
5
.
0
0
(
3
.
5
0
6
)
,
5
1
0
(
1
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0
1
8
3
)
;
A
,
n
a
l
.
C
a
l
c
.
f
o
r
3. Results and Discussion
C
H
C
l
N
S
I
r
P
F
(
7
6
4
.
1
9
)
:
C
,
3
6
, 3 . 6 3 ; N , 7 . 4 7 % .
.
1
5
;
H
3
.
5
6
;
N
,
7
.
3
3
.
2 3 2 7
4
6
F
o
u
n
d
:
C
,
3
6
.
2
7
;
H
3
.
1
S
y
n
t
h
e
s
i
s
o
f
c
o
m
p
l
e
x
e
s
2 . 5 e [(p-cymene)RuL2Cl]PF6 [5]:
m -1
Y
i
e
l
d
:
8
3
%
;
I
R
;
T h i o s e m i c ar b a z i d e l i g a n d s w e r e a l l o w ed t o r ea c t w i t h
t h e m et al p r e cu rs o r [ Ru (p - cy me n e ) Cl ] , [ Cp * R h C l ]
o r [ Cp * I rC l ] i n a 1 : 2 M r at i o i n m et h a n o l i n t h e
( KB
1
r
,
c
)
:
3
4
4
9 m( N - H ) ,
1
6
0
1
m
,
8
4
5
m
7
5
6
(
C
=
N
)
(
P
-
F
)
,
(
C
=
S
)
2
2
2
2
H
N
M
R
(
4
0
0
M
H
, J
z
,
C
D
C
l
,
p
p
m
)
:
1
1
.
3
5 (
, J
s
,
1
H
)
,
1
0
.
4
9
(
s
,
,
,
3
2
2
1
H
)
,
, J
9
.
8
4
(
d
,
1
H
=
1
,
6
H
z )
, J
,
8
.
0
7
(
d
,
1
H
=
4
H
z
)
,
7
.
8
7
(
d
p r e s e n c e o f N H P F . T h e n e w c o m p l e x e s 1 – 8 o f t h e
4
2
H
=
8
H
z
)
,
7
.
3
4
(
d
2
H
=
8
H
z
)
,
6
.
8
7
(
s
,
2
H
)
,
6
.
6
7
(
s
6

J. Chem. Sci.
(
2
0
2
0
)
1
3
2
:
3
4
P
a
g
e
5
o
f
1
0
3
4
g e n e r a l f o r m u l a , [ (a re ne )M ( r2( N L ) C l ]P F w e r e i s o - t h e N - H g r o u p s a r e n o t i n v o l v e d i n b o n d i n g t o t h e
,
S
)
6
3
2
,
4
5
l a te d a s c a t i on i c c o m p le x e s w i t h t h e ir h e x a fl u o - m et al s c en t e r.
T h e a zo me t h i n e p r o t o n o f c o m -
r o p h o s p h a t e s a l t s a s c o u n t e r i o n a s p r e s e n t e d i n p l ex es 1 – 4 w a s o b s er v e d a s a s i n g l et i n t h e d o wn fi e l d
S c h e m e 2 . A l l t h e s e m e ta l c o m p le xe s w e r e o b t a i n e d i n r e g i o n a t 8 . 7 1 , 9 . 6 1 , 9 . 8 2 a n d 9 . 9 5 p p m, r es p e c t i v e l y
g o o d y i e l d , a i r - s t a b le a n d n o n -h y g r o s c o p ic i n n a t u re . i n d i c a t i n g t h e c o - o r d i n at i o n o f t h e a zo me t h i n e n i t r o -
T h e c o m p l e xe s a r e s o l ub le i n p o l a r s o l v e n t s s u c h a s g e n t o t h e m et al c en t e r w h i ch a ri s e s d u e t o t h e d o n a -
a ce t o n e , a c et o n i t r il e , D M S O a n d D M F , b u t a r e i n s o l - t i o n o f l o n e p a i r s o f t h e e l e c t r o n t o t h e m et al c e n t e r .
u b l e i n n o n - p o l ar s o l ve n t s s u c h a s h e x a n e a n d d i et h y l T h e l i g a n d m et h y l p r o t o n s i g n a l f o r c o m p l e x es 5 – 8
e t he r . T h e s y n t h e s iz e d c o m p le x e s w e r e c h a r a c t er i ze d a p p e a re d a s a s i n g l e t a t 2 . 4 2 , 2 . 3 3 , 2 . 3 9 , 2 . 3 1 p p m
1
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p r o t o n s w e re a l l i n t h e e x p e c t e d r a n g e o f 9 . 8 4 – 6 . 5 6
p p m . C o mp l e x e s 1 a n d 5 d i s p l ay a s i n g l et a n d s e p t e t i n
t h e r an g e 2 . 1 7 – 2 . 4 3 p p m a n d 2 . 9 3 – 2 . 9 1 p p m c o r r e -
s p o n d i n g t o t h e m et h y l g r o u p a n d m et h i n e p r o t o n s o f
t h e i s o p r o p y l g r o u p o f t h e p - c y m en e l i g a n d . T h e s i g n a l
f o r t h e m et h y l p r o t o n s o f t h e i s o p r o p y l g r o u p i s
o b s er v ed a s o n e d o u b l e t a t 1 . 2 9 a n d 1 . 2 8 p p m f o r
c o m p l e x e s 1 a n d 5 . T h e r es o n a n c e f o r t h e s i x p r o t o n s
o f b e n z e n e i n c o m p l e x e s 2 a n d 6 w a s o b s er v ed a t 5 . 9 2
a n d 5 . 9 0 p p m. I n a d d i t i o n , a s i n g l et a t 1 . 6 5 , 1 . 6 6 , 1 . 5 6 ,
1 . 6 2 p p m i s o b s er v ed f o r c o m p l e x e s 3 , 4 , 7 a n d 8 ,
r e s p e ct i v e l y , c o r r es p o n d i n g t o t h e m et h y l p r o t o n s o f
t h e p e n t am e t h y l c y c l o p en t ad i e n y l r i n g .
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T h e p r e l i m i n a r y v a l id a t i on o f t h e c o m p le x f o rm a t i o n
c an b e c o n fi r m e d t o s o m e e x t e n t f ro m t he ir I R s p e c t r a
( F i g ur e S 1 – S 8, S u p p l e m e n t a ry I n f o r m a t i o n ) . T h e F T -
I R s p e c t r a o f t h e l ig a n d s s h ow b a n d s a r o u n d 3 4 0 0
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t o t h e N - H s t r et c h i n g f re qu e n c y . S p e c t ra o f t h e c o m -
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s t r e t c h i n g f r e q u e n c i e s, a n d i t h a s b e e n f ou n d t h a t t h er e
i s n o s h i f t i n t h e i r s t r e t c h i n g f re qu e n c i e s u p o n c o m -
p l e xa t i o n w h i c h m e a n t h a t t he N - H g ro u p d i d n o t f o r m
a n y b o n d w i t h t h e m e ta l i on . T h e a z o m e t h i n e ( C= N )
s t r e t c h i n g f r e q u e n c i e s o f t he f re e l ig a n ds w e r e
o b s e r v e d a t 1 6 3 9-1 6 6 7 c m- a n d a s h a r p b a n d w a s
o b s e r v e d a t 8 1 6 a n d 8 1 2 c m- , a s c r i be d t o ( C= S )
1
3
T h e C N M R s p e c t r a o f t h e c o m p l e x e s f u r t h e r
1
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e x p l ai n t h e f o r m at i o n o f c o m p l e x e s . T h e C N MR
s p e c t r a o f t h e r e p r es e n t at i v e c o m p l e x e s a r e p r o v i d ed
i n F i g u re s S 1 7 – S 2 1 , S u p p l em e n t ar y I n f o r m at i o n . T h e
1
1
3
C N M R s p e c t r a o f t h e c o m p l e x e s e x h i b i t ed s i g n a l s
1
r el a t e d w i t h t h e l i g a n d c ar b o n s , p - c y m en e l i g a n d c a r -
b o n s , r i n g c ar b o n o f b e n z e n e , m et h y l c ar b o n o f C p *
a n d r i n g c ar b o n o f C p * . T h e c ar b o n r e s o n a n c e o f t h e
t h i o c a rb o n y l ( C= S ) g r o u p a p p e a re d i n t h e l o we r f r e -
q u en cy r e g i o n a r o u n d 1 7 5 . 4 2 t o 1 8 0 . 7 0 p p m . T h e
a ro ma t i c c ar b o n s s i g n a l s f o r t h e l i g a n d s w e r e o b se r v e d
i n t h e r a n g e o f 1 2 0 . 0 2 t o 1 5 7 . 9 9 p p m . T h e m e t h y l ,
i s o p r o p y l c ar b o n a n d m et h i n e r es o n a n c e s o f t h e
p - c y m en e l i g a n d w e re d e t e c t e d a t 2 1 . 3 8 , 2 5 . 9 0 a n d
3 4 . 0 3 p p m . P ea k s a t 1 0 0 . 9 5 , 9 8 . 7 2 , 8 8 . 2 9 , 8 8 . 07 p p m
a s s i g n e d t o t h e a ro ma t i c c ar b o n o f p - c y m en e r i n g .
C o m p l e x e s 6 e x h i b i t ed a s h a r p p e a k a t 8 7 . 83 p p m
a s s i g n e d t o t h e c ar b o n o f b e n z e n e r i n g . T h e s i g n a l s
a s s o c i at ed w i t h t h e r i n g c ar b o n s o f t h e C p * l i g a n d w as
o b s er v e d i n t h e r eg i o n 9 1 . 3 3 t o 9 6 . 0 6 p p m , w h e r e a s,
t h e m et h y l c ar b o n r es o n a n c e s w e re o b s er v e d a s a
s h a r p p e a k i n t h e r an g e 7 . 8 8 t o 1 0 . 9 3 p p m. O v er a l l
r es u l t s f r o m t h e N M R s p e c t r a l s t u d i es i n t e n s e l y s u p -
p o rt t h e f o r ma t i o n o f t h e m et al c o m p l e x e s .
s t r e t c h i n g f r e q u e n c y o f t he l ig a n d s . T h e a z om e t h i n e
( C = N ) a n d t h e t h i o c a r b o n y l C = S s t r e t c h in g f re q u e n c y
o f t h e c o m p l e xe s w a s f o u nd i n t he r a n g e 1 5 9 9 – 1 6 3 7
1
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c m- a n d 7 5 5 – 7 6 6 c m- . A l l t h e v a l u e s a r e i n
4
4
a cc o r d an ce w i t h t he p r e v i ou s r e p o r te d . T h e c l e ar
s h i f t o f t h e tC a n d tC v ib ra ti o n b a n d s t o a l o w er
=
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f r eq u e n c y v a l u e s u g g e s t e d t ha t t h e t hi o s e m ic a r b az o n e
l i g a n d s c o o r d i n at e d t o m e ta l c e n t e r t h r o u gh a zo me -
t h i n e n i t r o g e n a n d t h i o c a r b o n y l s u l fu r. I n a d d i t i o n , a l l
t h e c o m p l e xe s s h o w d is ti n c t i v e s t r e t c h i n g f re q u e n c i es
1
f o r P - F c o u n t e r a n i on s i n t he r a n g e o f 8 4 4 – 8 4 9 c m - .
T o r a t i f y t h e f o rm a t io n a n d c o or d in a t i o n p at t e r n o f
1
m e t a l c o m p l e xe s t he H N M R s t u d i e s o f t h e l i g a n d s
a n d c o m p l e xe s w e r e r e c o rd e d i n d e u t e r a te d c h l o ro -
f o r m o r d i m e t h y l s u l fo x i d e a t r o o m t e m p e ra t u r e
1
( F i g ur e S 9 – S 16 , S u p p l e m e n t a r y I n f o r m a t i o n ) . T h e H
N M R s p e c t r a o f t he l ig a n ds , N - H p r o to n s a p p e a re d a t
1
1 1 . 5 7 a n d 1 0 . 61 p p m , r e s p e c ti v e l y , T h e H N M R
s p e c t r a o f c o m p l e x e s 1 – 8 e x h i b it t w o s i n g l e t i n t h e
r a n g e 1 1 . 3 6– 11 . 0 7 a n d 1 0 . 5 0 – 9. 7 3 p p m c o rr e s p o n d i n g
t o t h e t w o N H p r ot o n s a n d i ts s l i g h t ly s h i ft u p fi e l d
w i t h r e s p e c t t o t h e f re e l ig a n d i nd ic a t i ng t he c o - o r d i -
n a t i o n o f t h e l i g a n d t o t he m e ta l c e nt e r. T h e p r e s e n c e
o f t w o N - H s i g n a l s i n a l l t he c o m p le xe s s p e c i fie s t h at
T h e m / z v a l u es o f t h e r e p r es e n t at i v e c o m p l e x es a r e
l i s t e d i n t h e e x p e r i m en t a l s e c t i o n a n d a re p r e s e n t e d i n
t h e F i g u r e s S 2 2 – S 2 5 , S u p p l em e n t ar y I n f o r m a t i o n .
C o m p l e x e s 1 , 3 , 6 a n d 8 d i s p l a y t h ei r p r e d o m i n an t
p e a k s a t m / z : 5 2 7 . 0 6 2 , 5 2 9 . 2 0 5 , 4 8 5 . 1 1 7 , a n d 6 3 3 . 1 2 4
r es p e ct i v e l y c o r r es p o n d t o [ M - P F ]? i o n p e a k . T h e
6

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J. Chem. Sci. ( 2 0 2 0 ) 1 3 2 : 3 4
a n t i b a ct er i a l d e t e r mi n a t i o n , s o t h e s o l u t i o n o f a l l t h e
c o m p l e x e s w a s i n v e s t i g at ed i n D M S O . U V - V i si b l e o f
t h e c o m p l e x e s 1 – 8 w e re r ec o r d e d a t r o o m t e m pe r a t u r e
i n t h e r an g e 2 0 0 – 6 0 0 n m . T h e e l e c t r o n i c a b s o r p t i o n
s p e c t r a o f t h e l i g a n d s a n d c o m p l e x e s w e r e d e p i c t e d i n
F i g u r e s S 2 6 a n d S 2 7 , S u p p l em e n t ar y I n f o r m at io n . T h e
a n a l y s i s w a s p e r fo r me d b y m o n i t o r i n g t h e s o l u t i o n a t
d i ff e r en t t i me i n t e rv al s u p t o 4 8 h t o m i m i c t h e b i o -
l o g i c a l t e s t c o n d i t i o n s . N o c h a n g e s i n t h e U V -V i s
s p e c t r a w e r e n o t i c e d , s i g n i fy i n g t h at t h e c o m p l e x es a r e
s t ab l e i n D M SO s o l u t i o n .
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I n f e ct i o n s d u e t o d i ff e r en t p a t h o g e n i c b a c t e ri a a r e a
t e r r i b l e d a n g er t o h u m a n k i n d . D a n g e r o u s s t r a i n s o f
E. coli c an c au s e u r i n ar y t r a c t i n fe c t i o n s , g a s t ro e n t e r i t i s ,
a n d n e o n at al m en i n g i t i s . S. aureus i n fe c t i o n c a u s e s a
s e v e r e d i s e as e s t ap h y l o co c c a l s c a l d e d s k i n s y n d r o m e
( SS S S ) i n i n fa n t s a n d m as t i t i s i n c o w . K. pneumoniae
l e a d s t o t h e a w fu l d i s e as e p n e u m o n i a . T h e a n t i b a c t e r i a l
a ct i v i t y o f t h e l i g a n d s a n d i t s m et al c o m p l e x e s w er e
e v a l u a t e d a g a i n s t s e l e c t e d b a c t e ri a l s t ra i n s g r a m - p o si -
t i v e b a c t e r i a Staphylococcus aureus, t w o g r a m- n e g a t i v e
b a c t e r i a Escherichia coli, a n d Klebsiella pneumonia b y
u s i n g s t an d a rd t e c h n i q u e s , c i p r o fl o x ac i n w a s t a k i n g a s a
r e fe r en ce d r u g . E x p er i m e n ts f o r e ac h c o n d i t i o n w er e
p e r f o r me d i n t r i p l i c a t e . T h e s t ar t i n g p r e cu r s o r o f
[ ( ar e n e ) Ru C l ] , [ Cp * R h Cl ] a n d [ Cp * I rC l ] w er e
Figure 1.
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a p p e a r a nc e o f t h e s e p e a k s i n i ts m a s s s p e c t ra s t ro n g l y
s u p p o r t s t h e f o r m a ti o n o f c o m p le xe s .
T h e U V – v i s i bl e s p e c tr a o f c o m p le xe s 1 – 8 w e r e
r e c o r d e d i n 1 0 lM a c e t o n i tr i le s o l u t i o n s i n t h e r a n g e
2 0 0 – 6 0 0 n m . A l l t h e c o m p le x e s s h ow e d t hr e e b a n d s
a r o u n d 2 7 0 , 3 7 5 a n d 5 0 0 n m . T h e h i g h i nt e n s e b a n d
a r o u n d 2 7 0 n m i s a t t r ib ut e d t o n ?p* , b a nd a t t h e
l o w e r w a v e l e n g t h s a t 3 7 5 n m a s s i g n e d t o p?p*
t r a n s i t i on s. W h e r e a s , t he l ow e r e n e r g y a b s o rp t io n b a n d
i n t h e r e g i o n 5 0 0 n m a r e a s c r i b e d t o m e ta l t o l i g a n d
c h a r g e t r an sf er ( M L C T ) a r i s e s f ro m t h e e x c i t a t i o n o f
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e l ec t r o ns f r o m t he m e ta l t g l e v e l t o t h e e mp t y
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f o u n d t o b e i n ac t i v e a s r ep o r t e d i n t h e p r e v i o u s l i t er a -
3
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m o l e c u l a r o r b i t a l s p* l e v e l o f t he l ig a n d s ( F i g u r e 1) .
t u re . M e t al c o m p l e x e s o f t e n s h o w b e t t er b i ol o g i c a l
b a c t e ri a l a ct i v i t i e s a s c o m p a re d t o t h ei r l i g a n d s ; t h e r e -
f o r e , t h e f o r ma t i o n o f c o m p l e x e s i s g e n e r al l y a c c o m -
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T h e p o t e n c y o f a n a n t i b a ct e ri al a g e n t i s b a s e d o n t h e s i z e
o f t h e d i am e t e r o f z o n e s o f i n h i b i t i o n a g a i n s t t h e t e s t e d
b a c t e r i a l s t ra i n . T h e z o n e s o f i n h i b i t i o n ( mm ) o f t h e
c o m p o u n d s i n c o m p a ri s o n w i t h c i p r o fl o x a c i n w er e
g i v e n i n T a b l e S 1 ( Su p p l em e n t a r y I n f o r m at i o n ) a n d
g r a p h i ca l l y r ep re s en t e d i n F i g u r e 2. B o t h t h e l i g a n d s L 1
a n d L 2 s h o w s i g n i fi c a n t a ct i v i t y a g a i n s t g r a m- p o si t i v e
b a c t e ri a Staphylococcus aureus. H o w e v e r , i t d i d n o t
s h o w a n y n o t i c e ab l e a ct i v i t y a g a i n s t t h e g r a m- n e g at i v e
b a c t e r i a .
T h e s p e c i fi c c o n d u c t a n c e v a l ue s o f c o m p le x e s 1 – 8 o f
0 . 0 0 1 m ol a r c o n c e n tr a ti o n i n a c e t o n i tr i le s o l u t i o n s
w e r e r e c o r d e d a t r o om t e m p e r a t u r e a r e 2 2 1 , 2 4 8 , 2 5 3 ,
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v a l u e o f i o n i c c o n d u c t a n c e i s d u e t o t h e p r e s e n c e o f
i o n i c m oi e t i es . T h e s e r e s u l t s r e v e a l t he e l e ct r o l y t i c
n a t u r e o f m e t a l c om pl e x e s .
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D u e t o t h e i n ad e q u a te a q ue ou s s o l u b il it y o f t h e m et al s i ze d c o m p l e x e s ( e x c ep t c o m p l e x 1 ) s h o w p o t e n t
c o m p l e xe s, a n t i b a c t e ri a l a s s a y w e r e c a rr i e d o u t u s i n g a n t i b a ct er i a l a ct i v i t y , a mo n g t h e c o m p l e x e s e v a l u a t e d
s t o c k s o l u t i o n s p r e p a re d b y d i s s o lu ti o n o f t h e c o m - c o m p l e x 5 , C p * r h o d i u m c o m p l e x e s 3 a n d 7 s h o ws a
p o u n d i n D i m e t h y l S u l fo x i d e ( D M S O ) . T h e re i s a m ag n i fi c en t a ct i v i t y a g a i n s t a l l t h e t e s t ed b a c t e r i a l
p o s s i b i l i t y t h a t c h l or i d e l ig a n d o f m e ta l c o m p l e x e s s t ra i n . C o mp l e x e s 3 a n d 7 s h o w ed h i g h e s t a c t i v i t y
c o u l d u n d e r g o a l ig a n d e x c h a n g e w i t h t he D M SO a g a i n s t Staphylococcus aureus ( 1 5 0 . 2 2 m m a n d 1 6
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s h o w p o t en t a c t i v it y a g a i n s t Escherichia coli a n d e n h a n c e d b i o l o g i c a l a ct i v i t i e s .
Staphylococcus aureus. C o m p le x e s 2 a n d 6 , w h i c h a re
t h e b e n z e n e r u t h e n i um c o m p le xe s , s h ow m o d er a t e
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t e st e d o r g a n i s m s w a s t a k e n a s s t a n d a r d . T h e M I C &
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f r o m 0 . 01 5 t o 1 . 0 m g /m L a g a i n s t a l l t he t e s t ed
o r g a n i s m s. F o r Escherichia coli a n d Klebsiella pneu-
monia t h e M I C a n d M B C v a l ue o f c o m p le x 3 i s l e s s e r
t h a n t h a t o f c i p r o fl o x a c i n, f o r c o m p le xe s 4 a n d 7 t h e
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References
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I n s u m m a r y , w e h a v e s u c c e s s f ul l y s y nt h e s i z e d a s e r i e s
o f m o no n u cl e a r c om pl e x e s o f p -c y m e n e r ut h e n i u m,
b e n z e n e r u t he n i u m , C p * r ho d i um a n d C p * I r i d i u m
c o n t a i n in g t h i o s e m ic a r b a z i d e l ig a n d s . A l l t h e s e c o m -
p l e x e s w e r e o b t a i n e d i n g o o d y ie ld s a n d c h a r a c t e ri ze d
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s t r o n g l y s u p p o r t e d t he f o r m a t i o n o f t h e p r o d u c t .
S p e c t r o s c o p i c d a t a r e v e a l e d t h a t l ig a n d s c o or d i n a t e t o
t h e m et a l c e n t e r s t hr ou g h a z om e t hi n e n it r og en a n d
t h i o c a r b o n y l s u l f u r f o r m i n g a fi v e - m e m be re d c h e l a t e
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a ct i v i t y . M a x i m u m c o m p le x e s s h ow e d s i g n i fi ca n t
a n t i b a c t e r i a l a c t i v it y f or b o t h G r a m - p o s i t i v e a n d
G r a m - n e ga t i v e b a c t e ri a s i g ni f y i ng t he ir p o t e n ti al t o b e
d e v e l o p e d.
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