African Journal of Pure and Applied Chemistry Vol. 3 (9), pp. 170-176, September, 2009
Available online at http://www.academicjournals.org/AJPAC
ISSN 1996 - 0840 © 2009 Academic Journals
Full Length Research Paper
Vitamin B
12
models: Synthesis and characterization of
cyano bridged dicobaloximes and antimicrobial activity
Bakheit Mustafa Mohamed Salih and S. Satyanarayana*
Department of Chemistry, Osmania University, Hyderabad, 500007. Andhra Pradesh, India.
Accepted 15 June, 2009.
Reactions of the cyanide complexes of the type Co(CN)(DH)
2
L moiety (where L= thiourea, acetamide,
formamide, semicarbazide, pyrazole and aniline; DH = dimethylglyoxime) with the corresponding
benzyl(aqua)cobaloxime PhCH
2
Co(DH)
2
OH
2
gives a series of homometallic cyano-bridged compounds
of the type PhCH
2
Co(DH)
2
CNCo(DH)
2
L. All these complexes have been synthesized and characterized
by means of IR, LC/MS,
1
H,
13
C NMR and (C, H, N) analysis as well as their antimicrobial activities. The
formation of cyanide bridge is evident from the IR spectra by the appearance of (CN) shifts with
respect to the mononuclear parent complex.
Key words: Cyano-bridged, bimetallic complexes, antimicrobial activity.
INTRODUCTION
It is well known that the cyanide ion can connect two
metal ions as a bridging ligand. Linear cyanide-bridged
bimetallic complexes of the type M–CN–M have been
extensively studied (Rigo and Turco, 1974; Davies et al.,
1985; Mohan et al., 1987; Deeming and Proud, 1988;
Darensbourg et al., 1996; Ramsharan and Dikshit, 1993).
Cyanide-bridged, dinuclear transition metal compounds
are widely used in the areas of electron delocalization
and charge transfer studies (Zhou et al., 1990; Agnus et
al., 1989; Burewiez and Haim, 1988; Chrisstofides et al.,
1990; Scandola et al., 1993). The most successful and
often the sole strategy for preparing these materials still
consists in assembling building blocks, usually transition
metal complexes, one having potential bridging ligands
with another species possessing empty or available co-
ordination sites. This ambidentate behavior is evident in
cyanide compounds of the main group (Kawai and Kane-
saka, 1969) elements and transition metal complexes.
The-cyano bridged dimetal systems have been of interest
since the early recognition that ligand bridged complexes
play an important role in inner-sphere electron transfer
reaction (Paul and Alvin, 1976). For example; remarkable
degrees of metal-metal electronic coupling can be
observed across cyanide bridges (Scandola et al., 1993).
This synthetic strategy has been often utilized to
provide a general route to synthesize neutral dinuclear
*Corresponding author. E-mail: ssnsirasani@yahoo.com. Tel.:
91-40-23234231 or 09246521145.
cyano-bridged complexes and this strategy consists in
protecting the equatorial positions of the metal atoms with
a planar pseudo macrocyclic group and carry out ligand
substitution reactions on axial positions leading to bridge
formation, thus avoiding undesired side reactions usually
observed when preparing cyano-bridged complexes,
such as cis trans, isomerization (Ribas et al., 1980;
Ribas et al., 1979). In this study, we describe the synthe-
sis of cyano-bridged dinuclear complexes formed from
the reaction between the appropriate Co(CN)(DH)
2
L and
PhCH
2
Co(DH)
2
OH
2
fragment (DH = dimethylglyoxime).
Experimental
All chemicals and solvents used for the synthesis were of reagent
grade. Infrared spectra were recorded on Perkin-Elmer FTIR-1600
spectrophotometer in the range 4000-400 cm
-1
as KBr pellets.
1
H
and
13
C NMR spectra were recorded on a GE QE 300 NMR spec-
trometer at 25°C using a 5 mm broad band probe. Samples were
prepared by dissolving 25-50 mmoles in DMSO-d6. Elemental
analyses were carried out using a Perkin-Elmer 2400 elemental
analyzer.
Preparation of K[NCSCo(DH)2SCN
This complex was prepared by the method of Ablov and
Syrtosova (Ablov and Syrtsova, 1975; Crumbliss and Gaus, 1975)
which was converted to [NH3Co(DH)2SCN] by treatment with
concentrated NH4OH as described by Crumbliss and Gaus (1976).
This ammonia complex was treated with an equimolar amount of
KCN dissolved in minimum amount of water to obtain the salt K
[Co(CN)(DH)2SCN] in 80% yield. Then this potassium salt of cyano