ABSTRACT

In the field of organometallic chemistry, N-heterocyclic carbenes (NHCs) are considered to

be most illustrious class of coordination compounds for different purposes especially in
catalysis and pharmaceutical industry. Due to their facile synthesis and strong σ-donor and
weak π-accepter characteristics towards metal they produce stable adducts. In addition, these
organometallic compounds have proven to be better in efficacy and produced low
cytotoxicity as compared to pre-existing antimicrobial agents against different resistive
bacterial strains. Raman spectroscopic analysis has been used for that of characterization of
ligands and its organometallic complexes. In present research work, Raman spectroscopy will
be employed for the characterization of organometallic ligand and its Hg complexes. Raman
spectrophotometer with Peak Seeker Pro_785: Agiltron, USA will be sued for analysis.
Obtained results will be further processed via Matlab software 7.8 (Mathworks, U.S.A).
Principal components analysis (PCA) will be employed for further analyzing the Raman
spectral features of organometallic ligands and its Hg complexes. PCA reduces the
dimensionality and increase variability between ligand from its complex.

1. INTRODUCTION
N-heterocyclic carbenes (NHCs) are considered to be most illustrious class of
coordination compounds for different purposes especially in trans-metallation, storage mode
of H2, catalysis, dye sensitized solar cells, and pharmaceutical industry. Due to their facile
synthesis and strong σ-donor and weak π-accepter characteristics towards metal they produce
stable adducts. N-Heterocyclic carbenes (NHCs) are fascinating compounds with well-known
complexes. NHC complexes are almost in existance with each transition metal, as well as
their applications, particularly in catalysisDespite being one of the first NHC-metal
complexes to be discovered, mercury complexes are among the least studied of the many
NHC-metal complexes that have been discovered. Wanzlick and Schonherr reported the first
NHC mercury complex in 1968, which was made by reacting an imidazolium salt with a
simple mercury source, mercury (II) acetate. Mercury poisoning has been treated with
mercury (II)-bound 1,2-dithiolates like BAL4 (British anti-Lewisite, 2,3-dimercaptopropanol)
and some of its derivatives. Metal dithiolates and other organometallic chelates are used as
antibacterial, antifungal, antimalarial, antiviral (including anti-HIV) and antitumor agents in
medical science, as well as pesticides, fungicides, and bactericides in agriculture. Organotin
compounds have also been studied for their environmental and biological properties. Metal-
based NHCs complexes are synthesised using various protocols using their azolium halide
salts. Noble metals have long played an important role in human health, and their complexes
and salts are equally important for their excellent healing properties against a variety of
pathogenic diseases. Recent research has discovered that the biological activity of NHC
complexes is largely dependent on metal ions. NHC-metal complexes and their salts have
shown to have important wound healing and antimicrobial effects. The ease of derivatization
and strong stability of organometallic drugs were the most important factors in their growth.
Metal-based NHCs complexes are thus regarded as exceptional chemical moieties.
Furthermore, for the purposes of drug production and optimization, such complexes are
regarded as capable prerequisites. X-ray crystallography, Nuclear Magnetic Resonance
(NMR) spectroscopy, Fourier transform infrared (FTIR) and mass spectrometry
spectroscopies have all been used to characterise fine structure and determine organometallic
compounds. Notably, X-ray crystallography necessitated a large quantity of analyte in solid
form, and the high energy x-rays could cause the sample to be perturbed. Similarly, NMR
spectroscopy is thought to be an insensitive analytical instrument for low-concentration
analytes. Indeed, the benefits of these spectroscopic techniques are enormous, and they are
frequently used by researchers to obtain reliable characterization, especially for
organometallic complexes. Despite their specialisation, their use in the quick era is limited
due to the time-consuming and expensive steps of sample preparation, sample destruction,
and sample destruction. As a result, it necessitates and encourages the use of far more rapid,
simple, and low-cost methodologies. Raman spectroscopy can be used to characterise
chemical structures while also overcoming the drawbacks of other techniques due to its ease
of use, lack of sample preparation, low cost, and non-destructive properties. Raman
spectroscopy will be used in the proposed study to characterize various imidazolium salts and
their respective complexes, as well as to validate the formation of metal coordination
compounds, as well as a multivariate data analysis technique called Principal Component
Analysis (PCA). The PCA can trigger discrimination between different ligands and their
respective complexes based on Raman spectral data.

2. OBJECTIVES
 To sythesize organometallic complex of Hg with azolinium ligand and its
characterization using Raman spectrophotometer .
 To make utilization of Raman spectroscopy for further chemical products analysis
even from inorganic class.
  To demonstrate its use in finding of conformational or geometrical changes of
complex chemical species.
3. REVIWE OF LITERATURE

Raman spectroscopy has been successfully used in forensic sciences, pharmaceutical

industries, water analysis, food technology pathogenic detection, and clinical domain for
multiple disease diagnosis due to its many advantages, including speed, ease of use,
sensitivity, and reduced time. In recent years, Raman spectroscopy has been used less
commonly for the characterization of inorganic metal complexes, but this is changing as
high-performance instrumentation improves. The use of Raman spectroscopy to classify
inorganic form compounds has been demonstrated by acquiring a series of spectra for
complexes of classic transition metals at various pressures and temperatures.
[Hexaamminenickel chloride/nitrate compounds], tetrahedral or thermochromic square-planar
[tetrachloridocuprate(II)] complexes, square-planar [Plladinum (dithiocarbamate)2] and
[Platinum (dithiocarbamate)2] complexes, and the trans and cis [Copper (glycine-to)2] H2.
Similarly, other forms of compounds were also characterised including metal trans-dioxo and
metal-oxo complexes with electronic structure of d2, such as osmium (VI), rhenium (V) and
molybdenum (IV) (IV).

Between the coordinate covalent bond of metal and ligand, the difference in
symmetric stretching vibrational modes was presented as a function of temperature and
pressure changes. To obtain this purpose, Resonance Raman spectroscopy were used for
characterization of electronic structure for [Ru(benzoquinonediimine)(NH3)2Cl2] complex
by using 488 nm excitation wavelength with the examination of combination and overtones
bands. Time-dependent theoretical calculations were used to find properties at excited states
and rationalise the Raman intensities of this complex. Raman scattering can reveal a unique
molecular signature of inorganic metal complex chemical structures. This technique was used
to assess metal coordinate bond formation as well as to characterise their fine chemical
structural characteristics. Calcium-Oxydiacetic acid complexes were formed by the
complexation of Ca2+ and neutral oxydiacetic acid, and their structural characterization was
also carried out. Other researchers helped to prove the idea by successfully characterizing a
number of complexes, including [Li(XeF2)n]. Coordination of Ti and Si in silicotitanates
[(C5Ph5)CrX2]2 and (C5Ph5)CrX2(THF) (X = Cl, Br, I) complexes, as well as silyl
substituted fisher type carbene complexes (A = P, As, Ru, Ir).
 A group of researchers has made successful claims about the characterization of
carbonyl-metal complexes using Fourier transform Raman spectroscopy. Tricarbonyl (5-
cyclopentadienyl)-manganese(1),tricarbonyl-(5-cyclopentadienyl)rhenium(I),tricarbonyl(5-
methylcyclopentadienyl) manganese(I) (ll), and (6-benzene) tricarbonylchromium were
studied at room temperature with four different steroid hormones labelled with four different
model organometal. Also they proposed a classification of the much significant vibrations on
the basis of their relative peak intensities by using by using FT Raman measurements. The
main goal was to figure out which particular molecular vibrational modes related to the
steroid hormones in question would be good candidates for potential quantitative study.

The study or characterization of manganese-based complexes, such as [Mn(tris(1-

pyrazolyl)methane)(CO)3]Cl, which is known for its photo-induceable antitumor activity,
was published. They were able to validate the formation of the complex by looking at carbon
triple bond with oxygen (CO) stretching vibrations as a possible cancer cell marker. As a
result, CO showed Raman scattering in the range of 1800 to 2200 cm-1, which was found to
be useful in determining the metal carbonyl complex, even though the Raman signals for the
constituents of living cells are negligible.

4. MATERIALS AND METHODS

4.1. Chemicals

Chemical reagents and solvents will be purchased from analytical grade suppliers and
used in this research work as such.No need of further purification required. Chemical
regents used in this research work include 1-bromobutane,1-bromopropane,1-
bromohexane, mercury oxide, N-Butyl,1,4-Dioxane and imidazole.

4.2. Synthesis of complex

Salts/Ligands Synthesis

N-alkyl/aryl imidazole compounds will be prepared as described in the literature

(Starikova et al., 2003) with mild modifications in order to synthesise the desired ligands.
Furthermore, potassium hydroxide will be added to the already prepared imidazole solution
in DMSO, followed by vigorous stirring, and the sufficient alkyl/arylhalide will be added
dropwise in the same solution. Finally, the mixture will be added to water, and chloroform
extraction will be possible; thus, filter papers (Whatman) will be used to obtain dry extract.
The filtration method will be done two to three time.

Metal Complex Synthesis

The appropriate imidazolium salts will be dissolved in solvent (methanol) along with
HgO, and the mixture will be stirred until a clear crystal is formed, which will then be filtered
using Celite (545). After filtration, KPF6 will be dissolved in methanol in a separate round
bottom flask and applied dropwise to the already prepared mixture. As a result, metal
complexes with PF6- as the counter ion will be obtained as fine powder after drying at room
temperature.

4.3. Acquisition of Raman Spectra

Raman spectral acquisition will be accomplished with a Raman spectrometer

equipped with a Peak Seeker Pro-785 Model Agiltron from United States. The Raman
spectrometer is fitted with a charged coupled detector (CCD) and a monochromatic 785
nm diode laser as an excitation source.

4.4. Pre-Processing of acquired data

Matlab 7.8 (Mathworks, USA) and previously developed protocols will be used to
process and analyze Raman spectral data. Different algorithms will be used to preprocess
Raman spectral data, such as vector normalization, baseline correction, substrate removal,
and data smoothing.

4.5. Multivariate Data Analysis

The Raman spectral data of ligands and their respective mercury complexes will be
separated using principal component analysis (PCA). PCA would be used to reduce the
dimensionality of large data sets and increase their variability. PC1 explains the most
variability in the data set, and subsequent PCs explain the remaining variability.