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INTRODUCTION
CYCLOMETALLATION
Cyclometallation, discovered in the early 1960s. It has become one of the most popular
organometallic reactions, providing a straight forward entry to organometallic compounds that
feature a metal-carbon bond. Simultaneously, cyclometallation allows for the investigation of
the pertinent aspects governing the metal-mediated activation of unreactive bonds, especially
the CH bond. The reaction product is a metallacycle in which the metal is bound by a chelate
carboligand. Such chelation supports the generally highly susceptible MC bond and results in
organometallic compounds with increased stability. This enhanced stability may have been
relevant in the early discovery of the reaction, and may have spurred further developments , so
cyclometallation become one of the most convenient methods for creating a metal carbon bond.
Cyclometallation refers to the transition metal complexes in which a ligand undergoes an
intramolecular but rarely to intermolecular metallation with the formation of a chelate ring
containing a metal carbon sigma bond. For ligands containing aromatic groups bonded to donor
atom the cyclometallation reaction is known to be as ortho-metallation.




For examples Palladium(II) and platinum(II) have long been known to ortho-metallate
aromatic ligands such as azobenzene, benzylamines, and 2-phenylpyridines.

Azobenzene structure Benzylamine structure 2-phenylpyridine
E
H
M
H
E
M
+ HX

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These reactions are strongly influenced by substituent effects. Ligands that lack aryl
substituents will sometimes cyclometalate via activation of methyl groups, an early example
being the internal oxidative addition of methylphosphine ligands. Metallacycle formation
interferes with intermolecular C-H activation processes. For this reason, specialized "pincer
ligands" have been developed that resist ortho-metallation.
LATEST DEVELOPMENT IN CYCLOMETALLATION
a) Cyclometallation using d-block transition metals
Nowadays, cyclometallation using d-block transition metals is being fundamental aspects and
recent trends. Overview of the fundamental aspects of the cyclometalation reaction involving all
d-block transition metals. Cyclometallation has received considerable attention as the reaction
represents probably the mildest route for activating strong CH and CR bonds. Apart from the
genuine interest in the mechanism and scope of this fundamental bond activation process,
cyclometallation is a highly attractive and versatile synthetic method for creating organometallic
entities, with wide application potential. Furthermore, this review is limited on d-block transition
metals for cyclometallations only.
i) sigma -Bond metathesis
Cyclometalation reactions involving sigma bond metathesis has been considered as the
predominant pathway when CH bond activation is accomplished with electron-poor metal
centers such as high-valent early transition metals, and perhaps also with carbonyl complexes.
The generic process is depicted in Scheme A for a metal precursor comprising a CH3 ligand
and features a four-membered transition state. Analogous reaction coordinates apply for other
metal alkyl complexes and for hydrides.

L M CH
3
C H
3
H
E
M CH
3
E
C H
3
H
E M
L
CH
4

Scheme A


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Due to the significant electron density at late transition metal centers, the metal assists in
stabilizing the sigma complex (Scheme B). The process has therefore been termed sigma
complex-assisted metathesis (-CAM). Such a mechanism needs to be considered in various
cyclometalation reactions, especially those involving well-known rhenium, ruthenium, and
osmium hydrides as precursors for cyclometallation.

Scheme B
ii) Transcyclometallation (Special case)

The exchange of one cyclometalated ligand for another one, termed transcyclometalation,
represents a particular case of CH bond activation. Transcyclometalation involves MC bond
making and breaking, and depending on the sequence of these two events, may proceed either
through an inorganic intermediate (MC breaking before MC formation) or through a diorgano
metal complex (MC making prior to MC cleavage). Evidence for both mechanisms has been
obtained.
The reaction has been investigated in elegant work by Ryabov, who observed initial ligand
dissociation when reacting the palladacycle P in HOAc with phenylpyridine (Scheme C ).145The
reaction finally yields the cyclometalated complex Q and N,N-dimethylbenzylamine. Kinetic
results are in agreement with a dissociative pathway involving full release of the amine ligand
from the metal coordination sphere and formation of an inorganic palladiumintermediate.146
The first part of the reaction may be rationalized by metallacycle opening via decoordination and
protonation of the amine donor group in Q, thus transforming the chelate into a monodentate C-
bound ligand, which is highly susceptible to acidolysis. Subsequent cyclometalation may occur
with either of the two ligand precursors available, viz. phenylpyridine or dimethylbenzylamine,
according to the electrophilic pathways stipulated above. The product distribution qualitatively
correlates with the ligand-metal affinity . The reaction is under thermodynamic control and
similar equilibria are reached in transcyclometalations using benzylamine ligands containing
NMe2 and NEt2 donor groups, independently which of the two ligands is cyclometalated at the
outset of the reaction.147 Moreover, transcyclometalation experiments using polydeuterated
AcOH-d4 as solvent have indicated that deuterium is incorporated also into the non-metalated
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ortho-position of dmba.148 This H/D exchange suggests that cyclopalladation is an equilibrium
process in acetic acid and that PdC bond making and breaking is reversible.

Scheme C
b) Development of Functionalized Cyclometalated Ruthenium Chromophores for Light-
Harvesting Applications

Figure 1 : Dye synthesized solar cells
A series of bichromic cyclometalated bistridentate Ru(II) complexes containing a
triphenylamine-based donor unit produce broad, intense absorbance profiles. The ability to
modulate the redox behavior of each of the chromophore units independently was exploited to
converge on a high-performance class of dyestuff devoid of NCS ligands. The synthesis and
the electrochemical spectroscopic properties of asymmetrical bistridentate cyclometalated Ru(II)
complexes bearing terminal triphenylamine(TPA) substituent.

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The structural attributes were systematically modified for the series:
(i) electron-donating character of the terminal substituents (e.g., R
1
= H, Me, OMe)
placed para to the amine of the L-2,5-thiophene-TPA-R
1
ligand framework;
(ii) electron-withdrawing character of the tridentate chelate distal to the TPA-substituted
ligand (e.g., R
2
= H, CO
2
Me, CO
2
H); and
(iii) position of the organometallic bond about the Ru(II) center. UVvis spectra reveal
intense and broad absorption bands arising from a collection of metal-to-ligand charge-
transfer (MLCT) and TPA-based intraligand charge-transfer (ILCT) transitions that, in
certain cases, extend beyond 800 nm.
The importance of the findings.
This finding is important in that this arrangement confines the highest occupied molecular
orbital (HOMO) to the TPA unit rather than the metal, which is optimal for sensitizing TiO
2
;
indeed, a remarkably high power conversion efficiency () in the DSSC (i.e., 8.02%) is
measured for the TPA-substituted pbpy

chelate where R
1
= Ome. These results provide a
comprehensive strategy for improving the performance ofbistridentate Ru sensitizers devoid of
NCS

groups for the DSSC.

C) Synthesis and Characterization of Thorium(IV) and Uranium(IV) Corrole Complexes

The first examples of actinide complexes incorporating corrole ligands are presented.
Thorium(IV) and uranium(IV) macrocycles of Mes
2
(p-OmePh)corrole were synthesized via salt
metathesis with the corresponding lithium corrole in remarkably high yields (93% and 83%,
respectively). Characterization by single-crystal X-ray diffraction revealed both complexes to be
dimeric, having two metal centers bridged via bis(-chlorido) linkages. In each case, the corrole
ring showed a large distortion from planarity, with the Th(IV) and U(IV) ions residing unusually
far (1.403 and 1.330 , respectively) from the N
4
plane of the ligand.
1
H NMR spectroscopy of
both the Th and U 5xchang revealed dynamic solution behavior. In the case of the diamagnetic
thorium corrole, variable-temperature, DOSY (diffusion-ordered) and EXSY (5xchange)
1
H NMR
spectroscopy was employed and supported that this behavior was due to an intrinsic
pseudorotational mode of the corrole ring about the MM axis. Additionally, the electronic
structure of the actinide corroles was assessed using UVvis spectroscopy, cyclic voltammetry,
and variable-temperature magnetic susceptibility.

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The Importance of findings
This class of macrocyclic complexes provides a rich platform in an underdeveloped area for
the study of nonaqueous actinide bonding and reactivity.

Figure 2.0 : Corolle Ligands Complexes
d) Cyclometalated cis-Chelated Bidentate N-Heterocyclic Carbene Palladium Complexes:
Synthetic, Structural, and Catalytic Studies
Cyclometalated cis-chelated bidentate N-heterocyclic carbene palladium complexes derived
from binaphthyl-2,2-diamine (BINAM) have been successfully synthesized, and the
cyclometalated cis-chelated bidentate NHCpalladium(II) complex 5a has been characterized
by X-ray crystal structure diffraction. Moreover, researchers found that these novel
NHCpalladium(II) complexes are quite effective in SuzukiMiyaura coupling reactions and
FriedelCrafts reactions under mild conditions. The most active types of catalyst, palladium-
carbene complexes, were tested in pilot plant and proved to be industrially viable.
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Figure 3: Carbene Palladium complexes
Cross-coupling reactions using PdNHC (NHC= N-heterocycliccarbene) catalysts are discussed
in this critical review and examined in terms of catalytic activity and how these have permitted
advances in the area as they developed by referring to the diagram below.


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The importance of findings

The coupling reaction of aryl and heteroaryl boric acids with aryl and heterocyclic halides or
triflate is a powerful method for preparing various biaryl systems and is widely used in
synthesising natural products. The importance of the palladium-catalysed Suzuki-Miyaura
across-coupling reaction cannot be over stated in view of its general use in a variety of C-C
bond formations and is underscored by the large volume of research published in the last year,
include mg extension to aqueous and supercritical media and polymer-supported catalysts
Indeed, on a commercial scale the Suzuki-Miyaura reaction is usually preferred to other C-C
bond-forming processes since organo boric acids are conveniently synthesised reagents, and
are generally thermally stable and inert to water and oxygen. NHC ligands have been employed
with great success in this process .

e) Estimation of energy levels of new Iridium cyclometalated complexes via cyclic
voltammetry

Cyclic Voltammetry investigation of newly synthesized Iridium cyclometalated complexes
used for the first time as phosphorescent dopants in Organic Light Emitting Diodes (OLEDs).
The energy of the highest occupied molecular orbital (HOMO) and the lowest unoccupied
molecular orbital (LUMO) of complexes dissolved in acetomitrile were estimated on the basis of
theirs reduction half-wave potentials, taken from cyclic voltamograms and band gaps, obtained
from UV (Ultravioletvisible) absorption measurements. In this paper the obtained
HOMO/LUMO values of complexes are discussed in connection with electroluminescent
characteristics of OLEDs with hole transporting layer doped with the same complexes. The aim
of this research was to estimate the HOMO and LUMO energy levels of four new synthesized
Iridium cyclometalated complexes via cyclic voltammetry and discussed them in connection with
electroluminescent characteristics of OLEDs, where these complexes were used as dopants.

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Four new cyclometalated iridium diketonato complexes based on benztiasole ligands were
synthesized according to Scheme 1.


The importance of findings
Succesfully in designing, synthesizing and characterizing four new cyclometalated iridium
diketonato complexes, based on benztiasole ligands. This is estimated their HOMO, LUMO and
band gap by means of combination of cyclic voltammetry and UV absorption measurements.
The complexes were applied as dopants in OLEDs and it was established that depending on the
dopant concentration they were very useful for fine tuning of emitted colour.



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