CHAPTER I

INTRODUCTION

1.1 Coordination compounds

Coordination complexes was being synthesized and investigated after Alfred

Werner (1866-1919) who was the first scientist majorly contributed to the discovery
of this branch of chemistry by his coordination theory of metal-ammine complexes,
such as [Co(NH3)6Cl3] in 1913 [1]. The importance of coordination complexes in
our day to day life is increasing due to their complex structures and interesting
electronic, magnetic, biological and optical properties. Coordination compounds can
have widespread structures and applications depending on the ligands, metal ion,
coordination number and denticity. Many coordination compounds arise from
interesting ligand systems containing different donor sites. Therefore, the selection
of ligands plays a most vital role in determining the properties of coordination
compounds.

The development of the coordination chemistry has been three dimensional,

about breadth, depth and applications. The continuing respect for the evolving
science is apparent in the five Nobel prizes that have been interrupted heavily on the
subject (A. Werner, 1913; M. Eigen, 1967, Wilkinson and Fischer, 1973; H. Taube,
1983; Cram, Lehn and Pederson, 1987). The first (Werner) and last (Cram, Lehn and
Pederson) in the list recognized the old and the new realms of coordination
chemistry. The steady improvement in synthetic methodology allows seeing
coordination chemistry to enter a relative rather than investigative chemistry a
phase.

The development of complexes for application in catalysis is an obvious

example. Many metal complexes discovery applications in the field of catalysis [2].
Among the top performers in this class (and the elements involved) are the
Wilkinson catalyst for the hydroformylation reaction (Rh), olefin polymerization
(Zr, Ni) and the conversion of ethylene to acetaldehyde (Pd) and there are many
others too several to the discussion. One of the most significant current advances in

1
organic chemistry in asymmetric synthesis depends entirely upon transitional metal
atoms as the catalytic centers.

Several metal complexes also find applications in the field of medicine. The
use of metal complexes in therapy and diagnostic imaging is increasing. Throughout
history, both ancient and modern metal compounds have been used in medicine to
treat a variety of ailments, and a remarkable example is being cis-platin
(cisPtCl2(NH3)2, introduced by Rosenberg et al [3]. This discovery led to a veritable
avalanche of research in platinum chemistry and a continuing search for the most
effective anticancer drug [4-6]. Gold compounds like Auronofin, (2,3,4,6-tetra-o-
acetyl-1-thio-β-Dglucopyranoside-5) triethyl phosphine gold(I) [7, 8] are applied as
oral drugs against rheumatoid arthritis. The increasing applications of metal
complexes in various science fields are the driving force for the research and
development of coordination chemistry. In the present thesis, the coordination
chemistry of ruthenium metal is explored.

1.2 Ruthenium compounds

Ruthenium compounds, in general, are well-suited for several applications.

Ruthenium complexes have used as homogeneous catalysts because of their
excellent catalytic performance with good conversion and selectivity. The
ruthenium(II) catalytic systems bearing phosphine ligands have been reported to
whole many organic conversions in good yields conversion and selectivity [9, 10].
Ruthenium complexes are well known for their medicinal applications [11-21],
semiconductor applications [22], biosensors [23], as well as electrochemical
capacitors [24, 25] and photovoltaic devices [26].

1.3 Hydrazones

Schiff bases derived from hydrazines known as hydrazones are a class of

ligand that has been reported for their excellent ligating properties of the triatomic
group present in the basic structure of >C=N–N< (Figure 1). They are distinguished
from other class members by the two interlinked (–N–N–) nitrogen atoms.
Hydrazones possess a special place due to their ease of synthesis, easily tunable
electronic properties, denticity and a wide variety of complexes with catalytic,

2
structural, biological and industrial importance [27-30]. Hydrazone compounds
formed by the reaction of aromatic and heterocyclic hydrazides with mono and di-
aldehydes or ketones have exposed very versatile metal behavior. The functional
group of hydrazones causes these compounds to behave as bidentate ligands for
metal ion, and owing to the availability of -NH-C=N group, hydrazones show
(amido-imido) tautomerism (Figure 2).

Figure 1. General formation and formula of hydrazone

Figure 2. Amido-imido tautomerism

Hydrazone derivative is a class of important organic molecules, and they

could be used as valuable building blocks for the synthesis of bioactive natural
products and functional materials [31-35]. Therefore, the hydrazone-based
molecules have shown a wide range of biological properties such as
antiproliferative, amoebicidal, monoamine oxidase inhibitory, antiplatelet
aggregation, anti-microbial, insecticidal, EGFR inhibitory, anti-inflammatory and
analgesic activities [36, 37]. They have also been utilized as fluorescent sensors,
dyes, and chemical synthesis [38, 39]. Besides, the preparation of too crystalline

3
hydrazone derivatives is an effective method for the purification, isolation and
characterization of carbonyl compounds [40, 41]. As a classical approach for
synthesizing hydrazone derivatives, condensation of carbonyl compounds and
hydrazides is the most widely employed strategy, but it requires harsh dehydrating
conditions [42]. Some acid catalysts such as polystyrene sulfonic acid, SiO2/H2SO4,
glacial acetic acid, Mg(ClO4)2, polymer, zeolites, [Et3NH][HSO4], Dowex (strongly
acidic cationic exchange resin) chloride–oxalic acid [43-45], had been established to
promote this reaction.

1.4 N-Heterocyclic carbenes

N-heterocyclic carbene (NHC) are defined as heterocyclic species (nitrogen,

oxygen and sulfur atom) containing a carbene carbon and at least one nitrogen atom
within the ring structure [46-53]. Many different carbene compounds fall with
various substitution patterns, ring sizes and degrees of heteroatom stabilization [54-
56]. The general structures of N-heterocyclic carbenes (NHCs) are as shown in
figure 3.

Figure 3. Structural features of NHCs

N-Heterocyclic carbenes (NHCs) are currently recognized as key ligands in the

design of transition metal coordination complexes leading to a broad range of

4
applications, as shown in figure 4. The suitability of NHCs as ligands for transition
metals can be efficient by their intrinsic σ-donor ability with a standard sp2-
hybridized lone pair available for donation into a σ-accepting orbital of the transition
metal. The nature of bonding in the complexes has been studied by several diverse
groups and has been reviewed by González et al [57] and Cavallo et al [58]. While
σ-donation is the most significant metal-ligand binding component, the contribution
of both π-back-bonding into the carbene p-orbital and π-donation from the carbene
p-orbital may not be inconsiderable. For example, Frenking et al calculated that π-
contributions account for about 20% of the overall bond energy in group-11 metal-
imidazol-2-ylidene and imidazoline-2-ylidene complexes [59, 60]. In practice,
metal-C2 coordination is mostly drawn as a single rather than a double bond with π-
contributions restricted to delocalization within the NHC ring (often depicted by a
curved line between the ring heteroatoms). This representation best reflects the
experimentally observed potential for rotation around the metal-C2 bond and
emphasizes the differences between NHCs and conventional Fischer or Schrock
carbene ligands [61].

Figure 4. Major applications of NHCs coordinated to transition metals

1.6 Transition metal-catalyzed organic transformations

Transition metal (TM) catalysis goes to the furthermost significant chemical

research areas because many chemical reactions are catalyzed using transition metal
(TM) compounds. Various efforts were being carried by industry and academia to
find a new efficient catalyst for chemical processes. Transition metals (TM) play an

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essential role in catalytic research because they have verified huge diversity in
lowering the activation barrier for chemical reactions.

Amines are fundamental organic chemicals with widespread applications in

many research areas such as pharmaceutical products, agrochemicals, polymer
materials, industrial products [62]. Therefore, considerable efforts have been made
to the efficient synthesis of amines [63]. The alkylation of primary amines to form
secondary amines proved to be an affordable route, whereas the challenge on the
control of monoalkylation remains [64]. The older methods, such as hydroamination
[65], Ullmann reaction [66] and Buchwald-Hartwig coupling have been used to
synthesize compounds containing C-N bond. However, drawbacks, including pre-
functionalization step and requirement of stoichiometric excess amount of base and
generation of an equivalent amount of salt as waste, make the above methods
ineffective [67, 68]. Alternatively, the construction of carbon-nitrogen (C-N) bonds
catalyzed by precious metal such as ruthenium, iridium and palladium has become
prominent in recent years [69, 70]. The C-N bonds are formed by N-alkylation
reaction by coupling of amines with alcohols catalyzed by transition metal catalysts
via borrowing hydrogen methodology (BH) (Figure 5A) [71, 72]. Such reactions
release environmentally friendly solvent of water (H2O) as the only byproduct and
hence environmentally benign in addition to highly atom economical [73-79].

The construction of carbon-carbon bonds by α-alkylation of ketones with

alcohols, catalyzed by transition metal complexes, has occupied a special place in
synthetic organic chemistry [80]. Catalytic α-alkylation reactions were carried out by
enolates or enamines obtained from ketones with carbon electrophiles, such as alkyl
halides [81-84]. However, the pre-functionalization step and a stoichiometric excess
amount of base required for the above nucleophilic substitution generate an equivalent
amount of salt as waste [85-88]. These drawbacks prompted to develop of another
protocol to achieve the related objective. Borrowing-hydrogen methodology (BH) is one
of the methods that has been given concentration in recent years for alkylation of
ketones catalyzed by transition metal catalysts [89, 90]. In connection with BH
methodology (Figure 5B), hitherto Ru and Ir complexes have been used as the most
effective catalysts for alkylation of ketones with alcohols [91, 92].

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Figure 5. Proposed mechanism for borrowing hydrogen strategy in (A) N-
alkylation reaction (B) α-alkylation reaction

The amide bond is ubiquitous, and an amide coupling reactions account for
16% of all reactions performed in essential organic synthesis [93]. Heteroatom-
substituted derivatives are a necessary class of molecules due to their prevalence in
pharmaceuticals and related bioactive compounds. A recent survey of over 3500
drugs revealed that most alkyl amides feature an oxygen or nitrogen atom α, β, or γ
to the carbonyl. Generally preferred method to synthesis amide is by coupling
amines with acids. Moreover, alternative strategies, including studding ligation,
amino carboxylation of aryl halides, Schmidt reaction and Bachmann rearrangement,
are also used for amide bond formation [94]. However, the environmentally friendly
protocol for amide synthesis was the amide bond formation by borrowing hydrogen
(Figure 6A).

Figure 6. Proposed mechanism for borrowing hydrogen strategy in (A) amidation

reaction (B) β-alkylation reaction

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 One of the most widely used organic compounds in the industry and
laboratory is alcohols which is synthesized using various reported methods [95].
However, several limitations such as complicated procedures, usage of toxic
reagents, unavoidable side reactions and formation of inorganic salts as by-products
affect the utility of the reported synthetic methods. Therefore, efforts have been
taken to design a non-toxic and green alkylation methodology through readily
available precursor compounds [96]. Currently, the β-alkylation by hydrogen auto-
transfer process using transition metal catalyst is an attractive and workable method
for the preparation of coupled secondary alcohols. The β-alkylation is considered as
environmentally green since less toxic alkylating agents were used and water is the
only by product in this method (Figure 6B) [97]. This method follows a cascade
redox type pathway involving in situ dehydrogenation of the alcohol to the ketone or
aldehyde, followed by aldol reaction resulting in the loss of a water molecule and
subsequent hydrogenation of the resulting enone to yield the coupled secondary
alcohol as a product. Among the various transition metal complexes such as Cu, Ni,
Pd, Ru, Ir, Rh, and Fe used as homogeneous catalysts in β-alkylation reactions
[98,99], ruthenium catalytic systems bearing phosphine ligands have been reported
as eminent due to their high catalytic performance with high product selectivity.

The hydrogenation of esters to alcohols is one of the essential redox

transformations in organic chemistry. It is frequently used in natural product
synthesis to prepare organic building blocks and the industry to produce
agrochemicals, pharmaceuticals, fragrances and flavors [100]. The oldest method
generally preferred for the reduction of ester makes use of stoichiometric amounts of
dibutyl aluminum hydride or boron hydride (BH3), lithium aluminum hydride
(LiAlH4) in organic solvents such as diethyl ether or tetrahydrofuran (THF).
However, and undesirable characteristic brutal workup, procedures high costs, low
atom economy and safety affect the utility of above method [101-103].
Advantageously, in catalytic hydrogenations (H2) there were no side products
formed compared to the classic stoichiometric reduction [104, 105].

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 Based on the above, the work presented in this thesis deals with

• Design and synthesis of ruthenium(II) complexes encompassing

functionalized hydrazone or N-heterocyclic carbene ligands.

• Characterization of new ruthenium complexes with analytical,

spectral (FT-IR, 1H , 13C and 31P NMR, ESI-mass) and single crystal
XRD studies.

• Catalytic activities of the new complexes towards the synthesis of

pharmaceutically and industrially important simple organic
compounds.

1.7 Review of literature

In order to understand the nature of work, a brief history of previous works

was undertaken necessarily. A detailed literature survey on the synthesis, structural
characterization, and catalytic studies of transition metal complexes encompassing
hydrazones or N-heterocyclic carbenes (NHCs) is presented in this section.

Prakash et al [106] have prepared 1,3,4-oxadiazoles via a series of reactions

between salicylaldehydes and isoniazid. The ligand reacted with [RuHCl
(CO)(PPh3)3] in the presence of a base to give ruthenium(II) complexes bearing
‘salen’ type N, N-bis(salicylidene)hydrazone ligands (1–3). The ligand and
ruthenium(II) complexes were thoroughly analyzed by elemental analysis (FT-IR,
UV-Vis, NMR (1H & 13
C) and mass spectra as well as SC-X ray studies.
Additionally, the catalytic activity of the complexes for N-alkylation of amines with
alcohols was tested.

Ramachandran et al [107] have prepared new ruthenium(II) complexes. The

complexes were characterized by various spectroscopic and SC-X-ray studies. The
complexes were studied catalytic activity for N-alkylation reactions of amines with
alcohol.

Ruther et al [108] have reported new Ru-p-cymene complexes prepared from

tetracarboxylic acid ligands. The complexes were fully characterized by elemental

9
analysis, various spectroscopic studies and cyclic voltammetry. The solid-state
structure of one of the ruthenium complexes shows piano stool geometry around
ruthenium metal. The cyclic voltammetry studies revealed that the Ru(II/III)
oxidation processes occurred at 0.56-0.98 V depending on the ligand substitution.

Jayanthi et al [109] synthesized new ruthenium complexes from Ru-p-

cymene complex reaction with thiophene-hydrazide ligand in CHCl3–MeOH
medium. The two Ru complexes were characterized by spectral and single crystal X-
ray diffraction studies. From the DNA binding and quenching experiments, an
intercalative mode of binding with DNA was identified. The new complexes also
possess cytotoxic activity against cancer cells.

A family of Ru(II) complexes (Figure 7) were synthesized from

hydroxyquinoline–thiosemicarbazone-based ligands by Nirmala et al [110]. The
ligands and complexes analyzed by spectral studies. The Ru(II) complexes were
employed as a catalyst for organic reactions such as N-alkylation, aldehyde-to-amide
conversion and alkane oxidation. The maximum yield of amides was observed for
the substrate 4-nitrobenzaldehyde under optimized conditions.

Figure 7. Structure of Ru(II) hydroxyquinoline–thiosemicarbazone complexes

Half-sandwich ruthenium(II) complexes were synthesized by Vinoth et al

[111]. All the (η6-p-cymene) ruthenium(II) complexes were characterized by
elemental analysis and various spectral studies. The solid-state molecular structures
of the complexes revealed that the new complexes possess pian-stool geometry. The
synthesized ruthenium(II)-p-cymene complexes were used as catalysts for benzyl
alcohol coupling with a range of amines.

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 New ruthenium(II)-p-cymene complexes (Figure 8) with indeno isoquinoline
derivatives were synthesized and characterized by spectral studies. The complex
were determined by single-crystal X-ray crystallography. The complexes showed
cytotoxic properties against five cancer cell lines [112].

Figure 8. Structure of ruthenium(II)-p-cymene complexes with indeno isoquinoline

Pettinari et al [113] have synthesized three pyrazolone-based hydrazone

ligands reacted with half-sandwich complexes were characterized by spectral studies
and DFT calculations.

Das et al [114] have reported the application of transition metals in catalysis,

especially with the air-stable ligand. The synthesis of amines/imines directly from
amines and alcohol via hydrogen auto-transfer (HA) or acceptorless
dehydrogenation catalyzed by well-defined Mn complexes were reported.

Transition metal complex of complexes of hydrazone derivative from the

condensation of 2-aminobenzoylhydrazide and isatin have been synthesized by
Rekha et al [115]. The ligand and metal complexes were fully characterized by
elemental analysis, IR, NMR (1H & 13
C), 2D HETCOR and mass spectral studies.
The characterization studies revealed monoanionic tridentate coordination mode of
the ligand and octahedral geometry for Co(II), Cu(II) and Zn(II) complexes and
tetrahedral geometry for Ni(II) complex.

Synthesis, SC-X-ray diffraction studies and electrochemistry of a series of

DMSO containing Ru(II) hydrazone complexes (Figure 9) were investigated by
Alagesan et al [116]. The SC-XRD result revealed an octahedral geometry around
ruthenium metal. Electrochemical studies showed the metal centre, quasi-reversible,
one-electron redox behavior of the new complexes.

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 Figure 9. Structure of Ru(II) complexes with DMSO

Mondal et al [117] have reported the synthesis of Ni(II) complexes (Figure

10) were characterization by various spectroscopic and cyclic voltammetry studies
of these complexes was also reported. X-ray crystal structure determination of the
complexes revealed that four Ni(II) complexes had distorted octahedral geometry.
DFT calculations were used to recognize the nature of the frontier orbitals.

Figure 10. Structure of Ni(II) complexes

A new 3-acetylcoumarin thiosemicarbazone and its copper(II) (1), nickel(II)

(2) and zinc(II) (3) complexes have been synthesized by Rahman et al [118]. The
complexes fully characterized by FT-IR, UV–Vis, NMR (1H and 13
C), EPR and
mass spectroscopic studies. SC-XRD studies confirmed the solid-state structure of
the complexes (1 and 3). The interaction of the complexes (1–3) with bovine serum
albumin (BSA) and calf thymus DNA (CT-DNA) was explored using absorption
and emission spectral methods.

Kempe et al designed Co-PNP pincer catalysts based on a triazine backbone

that was highly active for the alkylation. This compound was exciting since in the
catalytic reaction, species with deprotonated anionic triazines appear to play an
important key role. Hanson et al [119] and Zhang et al [120] reported a Cobalt
catalyst, stabilized by a bis(phosphino)amine pincer ligand (Figure 11), which can
afford amines or imines depending on the reaction conditions. The groups of Feringa

12
et al and Barta et al [121], Wills et al [122], and Zhao et al reported [123] (Figure
12) the alkylation of alcohols with amines to give secondary amines by utilizing iron
catalysts.

Figure 11. Co(II) and Co(III) PCP pincer complexes

Figure 12. Efficient catalysts for the alkylation of amines with alcohols

Pincer (NNN) Ni(II) (Figure 13) catalyst was used for N-alkylation of amines with
secondary alcohols via hydrogen auto-transfer (HA) strategy. Several substrates with
different functional groups were abided by the pincer Ni(II) catalyzed N-alkylation
reaction [124].

Figure 13. Pincer-Ni(II) catalyzed N-alkylation reaction

13
 Dinda et al [125] have synthesized pyridyl hydrazone ligand by combining
pyrene-1-carbaldehyde moiety with 2-hydrazinopyridine. It’s coordinating behavior
towards [RhL(PPh3)2Cl2] have been examined. SC-X-ray diffraction studies have
verified the complexes (Figure 14) with a five-membered chelate ring in the
structure. Besides, theoretical exploration has been accomplished by time-dependent
density functional theory (TD-DFT) analyses.

Figure 14. Structure of ruthenium(II) complex

Chen et al [126] proved that the ruthenium complexes with 2-hydroxy

pyridyl fragment exhibited more catalytic activity for C-C bond formation of β-
alkylation of secondary alcohols with primary alcohols [127]. Himeda et al reported
an effective proton-responsive and water-soluble half-sandwich Ru-p-cymene
complex (Figure 15) [128-130]. Zhang et al said cyclopentadiene iridium complexes
showed more catalytic activity for hydrogenation [131].

Figure 15. Structure of half‐sandwich Ru complexes

A series of Ru complexes (1–6) of pyridine-carboxamide ligands and

ruthenium complexes have been synthesized by Vijayan et al [132]. All ligands and
ruthenium(II) complexes have been characterized by various analytical studies and

14
SC- X-ray diffraction studies. All ruthenium(II) complexes were showed a pseudo
octahedral geometry. This well-defined ruthenium(II) complexes have been used as
catalysts for the N-alkylation reaction.

The reaction between anthracene-9-carbaldehyde with 2-(phenylthio/seleno)

ethylamine results in Schiff bases (L) with [(η5-Cp)IrCl(µ-Cl)]2 followed by
treatment with NH4PF6, iridacycles of the type [(η5-Cp)Ir(L-H)][PF6] result (Figure
16). The ligands and complexes were characterized by NMR spectroscopic [ 1H, 13C
and 77Se] and HR-MS studies. Single crystal structures of ligand and the complexes
(1–4) were recognized with SC-X-ray studies. Moreover, all the iridium complexes
(1–4) acted as efficient catalysts or N-alkylation [133].

Figure 16. Structure of iridium complexes

Two new ruthenium(II) complexes [Ru(II)Cl(PPh3)2(L)] (1) and [Ru(II)(L)2]

(2) (Figure 17) were synthesized by Eswaran et al [134] in MeOH–CHCl3 and
characterized by elemental analysis, spectroscopic studies and SC-XRD data. In
vitro cytotoxicity assays against HeLa and MCF-7 cell lines showed better activity
of both the complexes.

Figure 17. Synthetic route of ruthenium complexes 1 and 2

15
 The ligand N-(2-isonicotinoylhydrazine-carbonothioyl)benzamide (H3L) and
its metal complexes with Co(II), Ni(II), Cu(II) and Zn(II) acetates have been
synthesized by Mohammed Hosny et al [135] and fully characterized by elemental
analyses, FT-IR, UV-Vis, NMR (1H & 13C), ESR, mass spectra, molar conductance,
effective magnetic moments and thermal analyses. The of the metal complexes were
measured by semiconductivity.

Ramachandran et al [136] have reported three new copper(I) complexes were

characterized by elemental analysis (FT-IR, UV-Vis, NMR (1H & 13
C), mass
spectral and single crystal X-ray diffraction studies. All the copper(I) complexes
used as suitable, efficient catalysts for the N-alkylation reaction.

Simple, robust, metal-free approach to the synthesis of N-acyl azoles from

both alcohols and aldehydes has been described by Ovian et al [137] amidation was
smoothed by commercially existing organic oxidant and proceeded under very mild
conditions to display structurally various substrates.

A rhodium-catalyzed oxidative amidation reaction has been developed with

sterically hindered aldehydes and alcohols for the synthesis of amides in superior
yields. [138].

Pedro et al [139] have prepared copper(II) and zinc(II) complexes with 2-

acetylpyridinenicotinichydrazone (HL). The ligands and complexes were
characterized by spectroscopic techniques (FT-IR, UV–Vis, NMR (1H & 13
C),
electron spray ionization (ESI) mass and conductivity measurements. Four
complexes (Figure 18) have been studied by single crystal X-ray diffraction four
complexes. Hirshfeld surfaces and compared to the 2D-fingerprint plots information
to the interactions upon the molecular packing.

Figure 18. Structure of copper(II) and zinc(II) complexes

16
 Pyrazole based palladacycle-phosphine (Figure 19) has been described by
Mamidala et al [140] and applied as a catalyst for the N-alkylation of sulfanilamide
and amines with alcohols via hydrogen borrowing strategy (HB) as well as catalytic
using N-alkylation reactions.

Figure 19. Molecular structure of palladacycle

A family of Co(II) complexes (Figure 20) have been prepared by Neslihan et

al [141]. The complexes were characterized by spectroscopic studies as well as
complexes was confirmed by SC-X-ray crystallography studies. Also, all the Co(II)
complexes were screened as a catalyst in N-alkylation reactions.

Figure 20. Structure of cobalt(II) complexes

Prakash et al [142] have prepared binuclear Cu(I) bis(salicylidene)hydrazone

complexes (Figure 21). Analytical and spectroscopic methods have characterized the
ligand and the Cu(I) complexes (1–4). SC-X-ray diffraction study of complex 2 has
been revealed a pseudo tetrahedral geometry around each Cu(I) center. The
complexes were used as a catalyst in N-alkylation of amines and alcohols.

Figure 21. Structure of copper(I) complexes

17
 Crabtree et al [143] have reported terpyridine ruthenium(II) complexes
(Figure 22a). [Ru(DMSO)4Cl2] (Figure 22b) as efficient catalysts for the synthesis of
primary amides in the presence of NH2OH·HCl and a base [144]. Williams et al
[145]. Further, a direct synthetic route for transforming aldehydes to primary amides
using FeCl3 in water has been described [146]. Recently, Singh et al have reported
ruthenium complexes (Figure 22 1a) as a catalyst for one-pot conversion of
aldehydes to primary amides in water medium [147].

Figure 22. Structure of ruthenium complexes

Chiral proline amine/amide ligands were synthesized by convergent reaction

starting from L-proline. The in situ formed new complex from the reaction of above
ligand and [RuCl2(p-cymene)]2 were evaluated as a catalyst for asymmetric transfer
hydrogenation of ketones in the presence of sodium formamide and sodium dodecyl
sulfate (SDS). The results revealed that activity and enantioselectivities strongly
depend on the N-substituents [148].

The cyclopentadiene functionalized iridium-N- heterocyclic carbene (Ir-

NHC) complexes have been reported by Peris et al for the β-alkylation of secondary
alcohols and N-alkylation of aniline [149]. Valerga et al reported the N-alkylation of
both aromatic and non-aromatic amines using Ru-(II)-picolyl-NHC complex as a
catalyst [150]. Recently, Huynh et al and Seayad et al have reported the N-
alkylation of amines with alcohols and diols using [RuCl2(p-cymene)(NHC)]
complex [151].

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 Figure 23. Structure of ruthenium complexes

Crabtree et al have reported the use of Iridium cyclopentadiene complex as a

catalyst for the N-alkylation of amines [152]. More recently, Fernández et al, Shan
et al and Rajaraman et al have used [RuCl2(arene)(NHC)] complexes (Figure 23) as
a catalyst for the formation of tertiary amines from primary benzylic alcohols and
cyclic secondary amines [153-155]. Şahin et al and Ozdemir et al have reported the
half-sandwich Ru-complexes bearing a chelating NHC-sulfonate ligand and the
chelating Ru-NHC-arene complexes as efficient catalysts for the N-alkylation of
aniline with benzylic alcohols [156,157].

A new series of novel pincer imidazolylphosphine ruthenium complexes

have been synthesized and thoroughly analyzed. The hydrogenation of benzonitrile
as a scale test identified [RuHCl(CO)(NImNHPtBu)] as the most active catalyst.
With its stable Ru-BH4 analogue a wide range of (hetero) aliphatic and aromatic
nitriles.[158].

Ramachandran et al [159] have prepared new series phosphine-

functionalized thiosemicarbazone ligands with ruthenium precursors to give
phosphine-functionalized thiosemicarbazone ruthenium complexes prepared (Figure
24). The ligands and complexes were characterized by elemental analysis and
various spectroscopic studies and single crystal X-ray studies. All the ruthenium
complexes were tested as a catalyst for N-alkylation reaction. Moreover, complex 2
was found to be a beneficial catalyst for N-alkylation reaction.

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 Figure 24. Structure of the ruthenium(II) complexes

New Ru-NHC complexes (Figure 25) were prepared by Ozdemir et al [160]

and characterized by NMR (1H and 13C), elemental analysis and single crystal X-ray
studies. The Ru-NHC complexes reported as a promising catalyst for β-CH bond
functionalization of tertiary cyclic amines.

Figure 25. Structure of ruthenium complex

Synthesis Ru(II) complexes containing salicylaldiminato functionalized
mixed NHC ligands and complexes (Figure 26) were described by Nirmala et al
[161]. The complexes have been characterized by elemental analyses and various
spectroscopic studies. The new complexes have been gauged as catalysts for the
selective hydration of nitriles to primary amides.

Figure 26. Structure of [Ru–NHC] complexes

Nirmala et al [162] have derived susbstitued imidazolium salts reacted with
ruthenium precursors to form Ru(II)-NHC complexes(Figure 28). The Ru(II)-NHC
complexes were characterized by elemental analysis and various spectroscopic

20
methods. The Ru-NHC complexes were catalysts using a variety of amides with
good yields.

Figure 27. Structure of Ru-NHC complexes

The synthesis of Ru(II) complexes with NHC ligands through in situ

transmetalation is described by Hollering et al [163]. The Ru(II) complexes were
evaluated for their catalytic properties in transfer hydrogenation reactions.

Donthireddy et al [164] have prepared imidazol-2-ylidene and 1,2,3-triazol-

5-ylidene containing ruthenium complexes. The Ru(II)-NHC complexes (Figure 28)
are an efficient catalyst for C-N bond formation across a wide range of primary
amine and alcohol substrates.

Figure 28. Structure of Ruthenium(II) N-heterocyclic carbene complex

Genc et al [165] have reported iridium(I) NHC complexes (Figure 29)

having benzylic wingtips. The new complexes used as catalysts in the β-alkylation
of secondary alcohols with primary alcohols.

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 Figure 29. Structure of Ir(I) NHC complex

Ru(II) complexes with both chelating of N-[1-alkylpyridin-4(1H)-

ylidene]amide and N-heterocyclic carbene (NHC) donor sites (Figure 30) has been
prepared by Leigh et al [166]. The complexes were characterized by UV-vis, NMR
(1H and 13
C) and cyclic voltammetry. The Ru-NHC complex used as the catalytic
activity of transfer hydrogenation.

Figure 30. Structure of ruthenium N-heterocyclic Complexes

A N,O donor-functionalized ligands have been synthesized by Vinoth et al

[167]. The prepared ligands were successfully utilized to access a series of Ru(II)
carbonyl complexes. All of the ligands and Ru(II) complexes were characterized by
various spectral studies. Additionally, the new bivalent Ru(II) azo compounds used
as catalysts in the synthesis of amides.

Schlepphorst et al [168] have synthesized new compounds with C-C bond by

α-alkylation of a wide range of ketones using a Ru(II)-NHC catalyst (Figure 31)
under BH methodology.

22
 Figure 31. Structure of ruthenium complex

The Ru- p-cymene complexes containing NHC and phosphine ligands were
synthesized (Figure 32) by Xieet et al [169] and fully characterized. The Ru-NHC
complexes were able to catalyze both dehydrogenative mono, diamination and
amidation synthesis selectively.

Figure 32. Structure of Ru-NHC Complexes

A family of palladium(II) complexes with NHC ligands were prepared by Jia

et al [170] and fully characterized by various spectroscopic studies. The SC X-ray
diffraction studies have determined the solid-state molecular structures of the
complexes. The palladium complexes utilized as a catalyst in quinolines synthesis.

Bai et al [171] have reported a new series of Ru-complexes as catalysts for

C-C bond formation by β-alkylation of primary alcohols with secondary alcohols
using ruthenium complexes.

23
 Ozdemir et al [172] synthesized Ru-NHC complexes and were thoroughly
analyzed by elemental analysis, NMR and single crystal X-ray studies. The Ru-NHC
complexes were used as catalysts in the synthesis of tertiary cyclic amines. The
catalytic products of tertiary cyclic amines were analyzed by 1H-NMR and 13C NMR
spectroscopic techniques.

Chakrabarti et al [173] have reported an atom economical BH methodology

for C–C bond formation using alcohols as alkylating agents. The Ru(II) complex
was a highly active catalyst for the β-alkylation of a primary alcohol with secondary
alcohols.

Premkumar et al [174] have synthesized Ru(II) carbonyl complexes by

salicylaldazine ligand reacting Ru(II)precursors [RuHCl(CO)(EPh3)3]. The ligands
and complexes have been analyzed by elemental analyses and various spectroscopic
methods. SC-X-ray diffraction studies have confirmed the solid structures of ligand
L1 and complex 1. Moreover, the ruthenium complexes (1-4) used as catalysts in
secondary alcohols.

Based on the above scenario, the present thesis scope focused on the
coordination behavior and catalytic activities of ruthenium complexes encompassing
hydrazone or N-Heterocyclic ligands. At the same time, the literature survey showed
that any other research group had not done the works presented in the thesis.

24
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