1

Literature Review on the Synthesis of

Ferrocene appended Organotin Compound

A Project Dissertation work submitted to the Department of Chemistry, Arya

Vidyapeeth College, affiliated to Gauhati University as a partial fulfillment of
requirements for the award of degree of the Master of Science in Chemistry.

Submitted by Under the Supervision of

Deizy Bharadwaj Dr. Dhrubajyoti Dutta

Roll No: PS-191-001-0074 Assistant professor

Registration No: 270511 of 2016-17 Department of Chemistry

M.Sc. 4th semester Arya Vidyapeeth College

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DEPARTMENT OF CHEMISRTY

ARYA VIDYAPEETH COLLEGE, GOPINATH NAGAR

GUWAHATI, ASSAM – 781016

CERTIFICATE BY THE SUPERVISOR

This to certify that Deizy Bharadwaj, student of M.Sc. 4 th semester in the

Department of Chemistry, Arya Vidyapeeth College has successfully completed
Her Project under my supervision. During this period, she worked on the title
‘Literature Review on Ferrocene appended Organotin Compound’.She puts her
sincere effort and has shown a great deal of enthusiasm; moreover, her conduct
was excellent.

Best wishes for her bright future.

Date: Dr. Dhrubajyoti Dutta

Assistant Professor

Department Of Chemistry

Arya Vidyapeeth College

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DECLARATION

I, Deizy Bharadwaj, hereby declare that the subject manner of the literature survey
entitled “Literature Review on Ferrocene Appended Organotin Compound” is
the record of original survey carried out by me at the Department Of Chemistry,
Arya Vidyapeeth College, Under Gauhati University, under the supervision of Dr.
Dhrubajyoti Dutta.

As the pandemic creating threat to all mankind, roaring across the globe I was not
able to access laboratory facilities and other facilities to develop own finding on
this topic.

To the best of my knowledge and belief, this literature materials written by

another person except where due reference is made within the survey itself.

DATE:

Deizy Bharadwaj

Roll no: PS-191-001-0074

M.Sc. 4th semester

Department of Chemistry

Arya Vidyapeeth College

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ACKNOWLEDGEMENT

In the pursuit of this academic endeavor, I would like to convey my heartiest

thanks and warm gratitude of my supervisor Dr. Dhrubajyoti Dutta, whose constant
support, valuable guidance that enable me to complete this survey. He encouraged
me through research and made every possible effort to bring the best out of me.

My words of gratitude and thanks to all the teacher of Department of Chemistry,

Arya Vidyapeeth College, for their advices and encouragement

My sincere thanks goes to all the lab assistant for their co-operation and
encouragement throughout and to my friends and well-wishers without whose
inspiration this project would never been materialized.

DATE:
DEIZY BHARADWAJ
Department of Chemistry
Arya Vidyapeeth College
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CONTENTS Pages

1.Introduction…………………………………………….. 6-7

2. Literature survey………………………………………. 8-25

2.1 Ferrocene appended organotin (IV) compound
2.2 Applications of ferrocenyl compound

3. Methodology and Spectroscopic characterization……. 25-29

4.Conclusion…………………………………………… 29-30

5.References……………………………………………… 30-33

1. Introduction:
 6

In 1951, two independent research groups first isolated ferrocene. It is a orange colored, air

stable compound and having melting point of 112 0C [1, 2]. The bonding in the molecule was

purely a result of either C-Fe σ-bonds or ionic interactions. In the following year, two

independent groups was elucidated the structure of ferrocene. As all the carbons were

electronically equivalent and, there was only one C-H stretching frequency observed in the I.R.

spectrum, Wilkinson concluded that all carbons must contribute equally in bonding to the iron

atom [2]. Fischer and Pfab [3] confirmed the proposed sandwich structure from X-ray diffraction

studies, and in which a central iron atom was located between two cyclopentadienyl rings. The

aromaticity of the compound was confirmed by Woodward, who performed electrophilic

aromatic substitution reactions, such as the Friedel-Crafts acylation with aluminum trichloride,

on the compound (ferrocene was found to react 3 x 106 times faster than benzene) [4].

The two cyclopentadienyl (Cp) rings of ferrocene may be orientated in two extremes of

either an eclipsed (D5h) or staggered (D5d) conformation. The energy of rotation about the Fe-Cp

axis is very small (~ 4kJmol-1) and the ground state structures of ferrocene may show either of

these conformations. Ferrocene can be considered as consisting of an Fe 2+ ion (six d-electrons)

bonded to two cyclopentadienyl anions (six π-electrons each), and thus it can be seen that

ferrocene obeys the 18-electron rule – all valence electrons are located in bonding or non-

bonding orbitals. The anti-bonding orbitals are left unpopulated, and hence the compound is

stable.

A more informative picture of the bonding within ferrocene is provided by a

molecular orbital ligand and metal orbitals. Symmetry considerations, the relative energies,
 7

overlap integrals of the ligand π-orbitals and the 3d, 4s and 4p orbitals of the central iron can be

used to predict which molecular orbitals will be formed.

Among metallocenes, ferrocene is the most important metallocene [5].

Metallocenes are metal complexes with (η5-C5H5‒) ligands called Cp, which occur in sandwich

structures as shown (Fig.1). The Cp ligand in ferrocene can undergo many reactions and is

possible to synthesis many ferrocene derivatives. There are many applications for ferrocene

derivatives. They are used as cancer treatment [6], as catalyst in many syntheses especially for

natural products [7] as well as polymer production [8]. The simplest carboxylic acid containing

ferrocene derivative is ferrocene carboxylic acid. Multimetallic and multimetallocene

assemblies, in recent times, are gaining more importance for a number of reasons [9]. In a

radically different approach to this type assembly, researchers, for synthesis, took help of

organotin chemistry [10, 11].

 8

M
X
M M
M
X X M X
X

a b c d

Fig. 1.1: sandwich (a), half-sandwich (b), multidecker sandwich (c) and bent-sandwich (d)

diagram.

2. Literature survey :

The three classes of organometallic complexes, metallocene diacidos, Cp2MX2,

Ferrocenium salts and organotin (IV) compounds have been reported to exhibit impressive in

vivo or in vitro antitumour activities against a range of tumour cell lines accompanied by a

different pattern of antitumour specificities and by a more favorable pharmacological and

 9

toxicological profile. The sufficiently robust metallocenes used for medical applications contain

metals from the iron and cobalt triad, with Fe, Ru and Co. The bent metallocenes typically

comprise metals, most importantly Ti, Zr, V,Nb, Mo in medical context. Interestingly, all

medicinally important bent metallocenes have a cis-dihalide motif, which is similar to the cis-

dichloro motif of the well-established anticancer drug cisplatin. This resemblance has spurred

interest in metallocenes in the medicinal inorganic chemistry, particularly through the work of

Kopf-Maier [1-3]. The antiproliferative properties of ferrocene sparked the development of

organometallic anticancer compounds [4-6]. Ferrocene by itself is not a particularly toxic

compound. Ferrocene can undergo a one-electron oxidation, yielding the ferrocenium cation.

This cation is rather stable and the redox reaction is reversible for the most ferrocene derivatives.

The success of the in vivo anticancer activity of some ferrocenyl-based molecules is encouraging

and this has inspired us to design new compounds of ferrocenyl derivatives with organotin (IV)

(main group metal) which is still unexplored.

2.1 Ferrocene appended organotin (IV) compounds:

Multiferrocenyl compounds have attracted considerable interest as multielectron

reservoirs, electron-transfer mediators, electrode modification materials, ion sensors, or as

multiferrocenyl compounds have attracted considerable interest as multielectron reservoirs,

electron-transfer mediators, electrode modification materials, ion sensors, or as materials for

electronic devices [18]. Ferrocenyl carboxylates (FcCOO-) containing organotin (IV) moieties

have been reported in the literature. (Ferrocene carboxylato-kO)triphenyltin (IV) was obtained by

the reaction of sodium ferrocenylcarboxylate and triphenyltin chloride [19]. Diffraction results
 10

indicated that the carboxylate oxygen atom bonds the tin atom in an anisobidentate fashion

giving a distorted tetrahedral geometry (Fig. 1.2) [18, 19].

In an another endeavor, the reactions of Ph3SnCl, ferrocene carboxylic acid and neutral

ligand such as 1,10-phenanthroline (phen) and 4,4ʹ-bipyridine (4,4ʹ-bipy) provided compounds of

compositions [(Ph3SnOC(O)Fc)(H2O)](phen) and [{Ph3SnOC(O)Fc}2(4,4ʹ-bipy)], respectively.

Crystal structure of [(Ph3SnOC(O)Fc)(H2O)](phen) reveals a distorted trigonal bipyramidal

geometry around the tin atom where the apical positions were occupied by the oxygen atoms of

the water molecule and monodentate carboxylate ligand while 1,10-phenanthroline molecule

reside in crystal lattice (Fig. 1.3) [20]. On the other hand, triphenyltin compound with 4, 4ʹ-

bipyridine contains two Ph3SnOC (O) Fc units which are linked through a bridging 4, 4ʹ-bipy

moiety. The phenyl groups form an equatorial plane while the oxygen atom belonging to the

carboxyl groups and the nitrogen atom from 4,4ʹ-bipy occupy the apical position in trigonal

bipyramidal geometry (Fig. 1.12) [20].

 11

The reaction of sodium ferrocenylcarboxylate with trivinyltin acetate yielded [Vin3SnOC (O)

Fc]n which is a one dimensional polymer with the carboxylato groups acting as bridge to the tin

units. The tin atoms are arranged alternately along helical chains around the screw axes of the

cell. The tin atoms are in trigonal bipyramidal arrangement with the vinyl groups in equatorial

plane and the oxygen atoms are in axial positions (Fig. 1.4) [21]. The same polymeric structure

was repeated for trimethyltin [22] and tributyltin [20] compounds, although they were

synthesized using two different methodologies. Trimethyltin and tributyltin compounds were

obtained by the reactions of triorganotin halide with ferrocene carboxylic acid in presence of

triethylamine and tetramethylammonium hydroxide, respectively

 12

On the other hand, the reaction of nBu2SnO with ferrocene carboxylic acid afforded an oxo-

bridged dimeric structure of composition [{[nBu2SnOC(O)Fc]2O}2].4C6H6 (crystallized from

benzene/ethanol) with four anisobidentate bridging carboxylate groups and has a planar tortuous

ladder geometry as shown in Fig. 1.5 [23]. Crystal structure of the un-solvated form of the same

compound i.e. [{[nBu2SnOC (O) Fc]2O}2] is also available in the literature [24] where the

crystals of the compound were obtained from DCM. In general, the dibutyltin (IV) compound

has a dimeric structure containing pseudo six- and pseudo seven coordinated tin atoms and can

be viewed as a centrosymmetric dimer [23, 24].

 13

Dibutyltin (IV) compound of composition [(μ-nBu2Sn)2(μ-nBu2SnOC(O)Fc)2(μ3-O)2-(μ-

OCH3)2]2was also studied by single-crystal diffraction analysis (Fig. 1.6) [20]. The molecular

structure reveals that there are two molecules in the asymmetric unit. Each unit displays a ladder-

type structural motif where all the tin atoms have distorted trigonal bipyramidal geometry.

FcCOO groups act as monodentate ligand. There are two tridentate oxygen atoms in each unit

which link two endo-cyclic tin atoms and one exo-cyclic tin atom. An additional links between

the endo- and exo-cyclic tin atoms are provided by bidentate deprotonated methanol that

formsthe asymmetrical bridges [20].

The reactions of the diorganotin oxide, R2SnO (R = Ph, tBu,nBu and Me) with ferrocene

carboxylic acid afforded derivatives of the types [{Ph2Sn[OC(O)Fc]2}2],

[{tBu2Sn(OH)OC(O)Fc}2], [nBu2Sn{OC(O)Fc}2] [24] and [Me2Sn{OC(O)Fc}2] [22]. The

dinuclear derivative [{Ph2Sn[OC(O)Fc]2}2] (Fig. 1.16) represents a new structural form of a

diorganotin dicarboxylates, [R2Sn(O2CR’)2]. In general, diorganotin dicarboxylates are

mononuclear compounds, in which the tin is six-coordinate arising from an anisobidentate

 14

chelating coordination mode of the two carboxylates. The molecular structure of the compound

contains two diphenyltin units and four ferrocene carboxylates (Fig. 1.7). The two tin atoms

present in the molecule are bridged by two ferrocene carboxylates. This results in the formation

of an eight-membered ring. Two-ferrocenyl moieties lie above and below the plane of the

Sn2C2O4 core. An interesting aspect of the molecular organization is that the phenyl substituents

present on one tin atom are found in an eclipsed conformation to those on the other tin atom.

Each tin atom in the compound is six-coordinated with a distorted octahedral geometry. The

axial positions are occupied by two phenyl substituents and the equatorial positions by four

carboxylate oxygen atoms (Fig. 1.7) [24]. On the other hand, two tin atoms in [{ tBu2Sn (OH) OC

(O) Fc 2 are bridged by two hydroxyl groups with a central Sn 2O2 stannoxane core and the

ferrocene carboxylate is monodentate. Thus, each tin atom is five-coordinated and has distorted

trigonal bipyramidal geometry (Fig. 1.7) [24].

In [nBu2Sn {OC(O)Fc}2], the two ferrocenyl moieties are attached to the tin atom through

the chelating carboxylate ligands. The tin atom has six-coordinate coordination environment and

the geometry around the tin atom is skewed trapezoidal bipyramidal (Fig. 1.8a) [24]. It is worth
 15

noting that in the asymmetric unit of [nBu2Sn{OC(O)Fc}2], one of the molecule of the two

ferrocene are on the same side of the plane containing the tin and the carboxylate oxygen atoms

while in the second molecule, the two ferrocene moieties are trans to each other [24]. The same

skewed trapezoidal bipyramidal geometry was observed in the case of its methyl analogue i.e.

[Me2Sn {OC(O)Fc}2] [22] but now the two ferrocene moieties are oriented in a trans manner as

observed in Fig. 1.8b.

A novel trinuclear n-butyltin cluster incorporating three ferrocene carboxylate

substituents of composition {nBuSnCl(O2CC5H4-Fe-C5H5)}3(O)(OH) has been synthesized by the

n
1:1 stoichiometric reaction of BuSn(OH)2Cl with ferrocene carboxylic acid. X-ray

crystallography results show that three tin atoms are connected by three bridging ferrocene

carboxylates whereas two of these tin atoms are hexa-coordinated; the third one is essentially

penta-coordinated with an additional weak interaction to chlorine bonded to one of the other tin

atoms of the same molecule Fig. 1.9 [25].

 16

Assemblies of a hexaferrocene unit on a tin-oxygen cluster with composition

[RSn(O)OC(O)Fc]6 (R = nBu, Bz) show a giant-wheel arrangement of the six ferrocene units

with a drum like stannoxane central core [26, 22], as shown in Fig. 1.10. There is also a distinct

cyclic connectivity of the six-ferrocene units linking tin atoms (Fig. 1.11) [26]. The ferrocene

carboxylate moiety is involved in binding to two alternate tin atoms of a distannoxane unit. The

central stannoxane cluster is made up of two hexameric Sn3O3 rings, each present in a puckered

chair-like conformation. These rings are joined to each other to afford six Sn 2O2 distannoxane

units as the side faces of the cluster [26].

 17

The reactions of RSnCl3 (R = 2-(phenylazo)phenyl) with FcCOOH in refluxing THF afforded a

dinuclear monoorganodistannoxanes [(RSn)2(μ2-O)(μ2-FcCOO)2(η-FcCOO)2].THF. The

molecular structure reveals that the tin atom has distorted pentagonal bipyramidal geometry.

A μ2-O unit, affording a rare Sn-O-Sn motif among monoorganostannoxanes, bridges the

two tin centers. In addition, one of the nitrogen atoms of the 2-phenylazophenyl substituent also

intramolecularly coordinates each tin. Further, the two tin centers are bridged by two

isobidentate ferrocene carboxylate ligands; each tin center also is bound by a chelating ferrocene

carboxylate ligand (Fig. 1.12) [27].

 18

Examples of organotin(IV) compounds with 1,1ʹ-ferrocene dicarboxylic acid are also

available in the literature. The coordination polymers containing ferrocene backbone have been

studied in detail [28]. In this pursuit, the reaction of 1,1ʹ-ferrocene dicarboxylic acid with

bis(triphenyltin) oxide afforded a molecular heterobimetallic compound of composition

[(Ph3Sn)2({OC(O)}2Fc)]. Two carboxylate groups are involved in an anisobidentate chelating

coordination mode to two triphenyl tin units (Fig. 1.13). Further, to utilize the vacant

coordination site in the compound [(Ph3Sn)2({OC(O)}2Fc)], the above reaction was repeated in

the presence of monotopic nitrogen ligand (4-picoline) and ditopic nitrogen ligands (4,4ʹ-

bipyridine, 4,4ʹ-trimethylenebipyridine and 4,4ʹ-vinylenebipyridine) [28]. 4-picoline afforded a

discrete pyridine-coordinated dinuclear molecular compound [(Ph3Sn)2({OC(O)}2Fc)(4-pic)2]

where the geometry around tin is trigonal bipyramidal with the axial positions being occupied by

an oxygen donor atom from the carboxylate ligand and a nitrogen donor atom from 4-picoline

(Fig. 1.14). In contrast, when the reaction was carried out in the presence of ditopic nitrogen

ligands, the compounds of compositions [(Ph3Sn)2({OC(O)}2Fc)(-(4,4-bipy))]n,

[(Ph3Sn)2({OC(O)}2Fc)(-(4,4-tmbipy))]n and [(Ph3Sn)2({OC(O)}2Fc)(-(4,4-vdipy))]n (4-pic =

 19

4-methylpyridine, tmbipy = 4,4-trimethylenebipyridine, vdipy = 4,4-vinylenedipyridine) were

isolated as nitrogen-bridged one-dimensional coordination polymers. The backbones of the

polymers contain three distinct structural components viz., two triorganotin units, a ferrocenyl

unit and a ditopic ligand containing two terminal nitrogen donor centers that interconnect the

Sn2/Fe motifs (Fig. 1.15) [28].

On the other hand, trimethyltin and tributyltin afforded 2D-coordination polymers of

compositions [(Me3Sn)2({OC(O)}2Fc)]n and [(nBu3Sn)2({OC(O)}2Fc)]n, respectively. These

polymers are formed as a result of anisobidentate bridging coordination modes of the two-

carboxylate units of the ligand. The coordination geometry around tin is trigonal bipyramidal.

Interestingly, the 2D-coordination polymers contain 24-membered macrocycles; each of which is

comprised of four trialkyl tin units (Fig.1.16) [28].

 20

Ferrocene dicarboxylates-bridged redox-active diorganotin compounds viz.,

[nBu2Sn({OC(O)}2Fc]2 and [Bz2Sn({OC(O)}2Fc]2 have also been reported [29]. The molecular

structures show that the tin atom within the macrocycles is bridged to each other by two

ferrocene carboxylate ligands giving rise to a heterobimetallic tetra nuclear 16-membered

macrocycles. The tin atoms have skewed trapezoidal bipyramidal geometry (Fig. 1.17) [29].

Organooxotin cluster incorporating inorganic spacers between two ladders each

containing five tin atoms of composition [(Bz 2SnO)3(Bz2SnOH)2({OC(O)}2Fc)]2·10H2O has been

synthesized and characterized crystallographically [30]. As can be seen in Fig. 1.18, the two
 21

ladder clusters are connected by two ferrocene dicarboxylates dianions. The ladders are in

different planes, which are almost parallel to one another. The 1,1ʹ-ferrocene dicarboxylates

dianions adopt a mutually trans- orientation to minimize repulsions between the organic groups.

The separation between the two ladders is at least 10 Å, which indicates that the compound

constitutes a nano sized tin-oxygen cluster [30].

A mixed-valence tin-oxygen cluster containing six peripheral ferrocene units has been

synthesized by the reaction of nBu2SnO and 1,1ʹ-ferrocene dicarboxylic acid. Diffraction studies

revealed that the molecule has a Sn8O4 core (Fig. 1.19). Four endo- tin atoms and four μ4-O

atoms occupy the corners of a distorted cube. Each face of the cube is defined by a four-

membered Sn2O2stannoxane ring. Furthermore, each μ4-O atom is coordinated to one exo- Sn

atom to form a Sn8O4 cluster. Iron of the ferrocene occupies the vertices of a regular octahedron

[31].
 22

2.2Applications of Ferrocenyl compounds

Because of the well-defined electrochemical and spectroscopic behaviour, chemical

stability and low toxicity of ferrocene, it has found applications in areas such as anion sensing,

asymmetric catalysis, as a mediator between redox enzymes and electrodes, as liquid crystalline

materials, in materials with high second harmonic generation efficiencies for non-linear optics

and also as anticancer agents. The incorporation of a ferrocene moiety into biomolecules is

currently an area of intense research activity. Owing to the ease with which electrophilic

aromatic substitution can occur on the cyclopentadienyl rings, a vast array of ferrocene

derivatives have been reported in the literature since it was first discovered over fifty years ago.

During the last twenty years, there has been an increasing use of ferrocene derivatives as

chiral auxiliaries in homogenous asymmetric catalysis, both in research and on an industrial

scale. The ferrocene moiety offers many advantages in this respect. A chiral, redox-active ligand

is, in theory, capable of acting as a chiral auxiliary in an organic transformation, with subsequent

decomplexation of the ligand upon electrochemical oxidation, thus facilitating the catalytic

cycle. Due to its bulkiness, a ferrocene nucleus adjacent to a stereogenic centre can improve
 23

stereoselectivity via steric hindrance, and nucleophilic substitution reactions at positions vicinal

to the ferrocene group are highly favoured, and take place with retention of configuration [32].

Two such ligands (1, 2), have been synthesised by Chesney et al. (derived from L-(S-

methyl)-cysteine and L-methionine respectively), and were shown to be particularly effective in

palladium-catalysed substitution reactions of allylic acetate with diethyl malonate [33]. The

ligand derived from L-methionine proved to be more effective in transferring chirality than that

derived from S-methyl-L-cysteine, probably due to the extra methylene group between the donor

atoms which co-ordinate to the palladium atom. The effect of this is to bring the asymmetric

environment closer to the allyl species.

Gonzales reported the synthesis of palladium complexes with chiral ferrocenyl-

thiazolidines, again utilizing S-donor atoms derived from L-cysteine. The arrangements of the

ligands in the complex is similar to those described for other palladium (II) complexes of the

type [Pd(η3-C3 H5)(Br)(L)] which have catalytic activity [34].

 24

The Schiff-base derivatives prepared by Lopez have also proved to be effective donors in

palladium and platinum complexes, and the group synthesized a di-μ-chloro-bridged

cyclopalladated complex [35].

Orthometallation is a common feature of heterobimetallic systems incorporating a

ferrocene moiety. This process involves the chelation-controlled, regioselective C-H activation

with a metallation reagent, resulting in the formation of a new metal-carbon bond [36]. The

cyclometallation of ferrocene results in the formation of planar, cyclometallated derivatives,

which have great potential in the area of asymmetric catalysis [37].

The design of ferrocene-based anion receptors is another area of current intense research

[38, 39]. In biological processes, the majority of enzyme substrates are negatively charged [40].

Therefore, an understanding of the interactions, which bind the guest and host molecule together,

has potential application in the design of drugs capable of mimicking those interactions.

Alzheimer’s disease has been linked to anion-binding enzymes, and cystic fibrosis is known to

be caused by a misregulation of chloride channels. From an environmental point of view,

pollutants such as phosphate and nitrate anions need to be continually monitored [41].

Bioorganometallic chemistry is currently of interest to many research groups, and

incorporates areas ranging from inorganic to medicinal chemistry [42]. Ferrocenyl amines have

also been shown to have antiproliferative properties against a variety of carcinomas and tumors

[43]. Cisplatin analogues with ferrocenylamine ligands have been prepared by Duffy and co-

workers [44]. This study highlighted the relationship between the toxicology of ferrocenyl

amines and their basicity. N-alkyl ferrocenyl amines were observed to protonate and oxidise to

their ferrocenium analogues more readily than N-aryl ferrocenyl amines. Protonation competes
 25

with complexation to the Pt (II) center, and the reduced biological activity of the N-alkyl species

in vitro is attributed to their propensity to protonate [45].

A series of heterobimetallic complex of ferrocene have shown anticancer property [46]

towards embryonic kidney (HEK-293T), breast (MDA-MB-231), and lung (A-549) cancer cells.

Fc has been used as a scaffold for new ligands and then coordination of Fc ligands with other

metals affords heterobimetallic compounds with varied geometries, oxidation states, and

electronic properties, which may eventually afford interactions with biological targets and

chemotherapeutic applications. In view of the early accomplishment of possible cytotoxic

properties of ferrocene-appended organotin (IV) compounds, a series of structurally

characterized ferrocene were synthesized. In vitro cytotoxic activities of two groups of

compounds, viz. triphenyltin derivatives and tributyltin derivatives were assessed by an MTT

assay against human hepatic carcinoma (HepG2) cells, and the observed activities are much

higher in comparison with Fc and respective metallo proligands FcLnH. This observation

suggests that the organostannyl moiety is the activity-determining factor and may possess a

synergetic effect with the ferrocene accompaniment [46]. Cyclic voltametry studies were

performed for Proligands and compounds exhibited a one-electron reversible anodic wave vs

SCE assigned to the Fe (II) → Fe (III) oxidation process. The oxidation potential values for the

compounds are generally higher than that of ferrocene in the same solvent and lower than that of

acetylferrocene, indicating the cyclopentadienyl substituents in the compounds of this study are

weaker net electron donors in comparison to the H substituent, though better than the acetyl

group [46].

Cyclic voltammetric studies were carried out on a series of compounds [29].

Electrochemical studies on organostannoxane- supported assemblies such as [n-

 26

BuSn(O)O2CFc]6, [n-BuSn-(O)O2CCH2Fc]6, and [n-Bu2Sn{OC(O)Fc}2]2 showed a single quasi-

reversible oxidation. Although the nature of the organostannoxane core varied in these

compounds, the oxidation peak potential of the ferrocene periphery remained virtually invariant.

This suggested a complete absence of electronic communication between the various individual

ferrocene units present in these assemblies. In contrast, in the current study we have observed

some compounds showed two quasi-reversible single electron oxidations. The extent of

electronic communication between the two-ferrocene units be assessed by examining their

comproportionation constants [29].

3. Methodology and Spectroscopic characterization :

It is planned to synthesize a great variety of newer classes of suitable molecule containing

organotin and organ iron combining the anti-tumoral properties of both and to evaluate the

pharmacological profile based on in vivo and in vitro studies. For this purpose, several

complexes will be designed and synthesized adopting suitable synthetic methodologies. A

systematic variation of chelating center by suitable modifications in ligand would provide further

scope for obtaining new ligands and complexes.

Ferrocene (as well as other metallocenes) are usually prepared by one of three different

synthetic routes. The first of these involves the cracking of dicyclopentadiene (a retro Diels-

Alder reaction), followed by deprotonation of the weakly acidic cyclopentadienyl with an alkali

metal. Treatment with iron (II) chloride then affords ferrocene:

 27

The second method is known as metal vapors synthesis; the reactants are heated to high

temperatures, and then brought together on a cold surface:

Finally, ferrocene can also be prepared via the use of an auxiliary base, which generates the

cyclopentadienyl anion in situ:

A general method was followed for the synthesis of ferrocene-appended triphenyltin

compounds [46]. In a typical procedure, a mixture of Ph 3SnOH and the appropriate metallo pro-

ligands FcLnH in a 1:1 stoichiometric ratio was heated to reflux in anhydrous toluene (50 mL)

for 8 h in a round bottom flask equipped with a Dean−Stark apparatus and a water-cooled

condenser. The reaction mixture was filtered while hot, and the solvent was removed using a

rotary evaporator. The residue was washed, boiled with hexane, filtered, and dried in vacuum.

The residue was recrystalised using appropriate solvent(s) to yield the desired product. An

analogous procedure was followed for the synthesis of the tributyltin(IV) compounds but using

(Bu3Sn)2O and FcLnH in a 1:2 stoichiometric ratio. The synthesized ligands were characterized

by IR, 1H, 13C and 119Sn NMR spectroscopy. Most of the complexes were further characterized by

single crystal X-ray crystallography [46]. Representative molecular structure of some complexes

were shown below-

 28

A hexaferrocene assembly can be obtained by reaction of suitable reactants by stirring

conditions and the molecular structure is shown below.

 29

Chandrasekhar and his group reported the reaction of 1,1¢-ferrocene dicarboxylic acid,

LH2, with diorganotin halides R2SnCl2 (R ) n-Bu and Bn) or Ar2TeCl2 (Ar ) 4-OMe-C6H4) in the

presence of triethylamine afforded, in nearly quantitative yields, heterobimetallic tetra nuclear

macrocycles [R2SnL]2 and [Ar2TeL]2. The molecular structures of these compounds have been

confirmed by single-crystal X-ray analysis and show that the two main group metal atoms within

each macrocycles are bridged to each other by two ferrocene carboxylate ligands. In the case of

the organotin derivatives, the ferrocenedicarboxylate ligand acts in an anisobidentate chelating

manner, leading to a hexacoordinate tin present in skewed trapezoidal bipyramidal geometry. In

contrast, in the tellurium analogue the ferrocene carboxylate ligand is monodentate, leading to a

tetra coordinate tellurium in a seesaw geometry shown below. ESI-MS studies on these

macrocycles complexes reveal that they retain their structural integrity in solution [29].
 30

Recently, a series of four new long chain triorganotin (IV) esters containing a diazenyl-

and an imino-groups appended with ferrocene scaffold were designed and synthesized [47].

Ferrocene based metallo proligands H'HFcL1 and H'HFcL2 were obtained by reacting isomeric

3-/4-ferrocenylanilines with 2-[(E)-2-(3-formyl-4-hydroxyphenyl)-1-diazenyl]benzoic acid,

which upon reactions with appropriate triorganotin(IV) precursors yielded compounds namely,

[nBu3Sn(HFcL1)] 1, [Ph3Sn(HFcL1) 2, [nBu3Sn(HFcL2)] 3 and [Ph3Sn(HFcL2) 4. Compounds

1−4 have been characterized by elemental analysis and their spectroscopic properties were

investigated using IR, UV-Vis and NMR spectroscopic techniques. The molecular structures of

H'HFcL1 and two representative heterobimetallic compounds 3 and 4 have been determined by

X-ray crystallography. Compound 3 is a 1D polymer and 4 is a discrete molecule 9 (shown

below); their structural differences relative to those of H'HFcL 1 clearly indicate the influence of

the binding of the tin cluster. The redox properties of the metallo pro-ligands and their

compounds were also investigated by cyclic voltametry [47].

 31

4.Conclusion:

Organometallic compounds are finds a bigger range of technical and industrial applications

than the organic compounds of any other metal. Many of these applications involve catalysis and

anti catalysis often in polymer chemistry. In this review, we are able to study lots of field where

many applications of ferrocene and organotin are found. Organotin compounds have a lot of

biological and pharmaceutical applications. Moreover, ferrocene are also considered as very

advantage of Metallocene. The current investigation deals with the method of synthesis and

characterization of the complex that we have got form the various research paper. In this review,

we discuss about the various methods of ferrocene appended organotin compound. It gives a lot

of information about the complex, which helps in our daily life too.

With due respect, I want to state that the project presented by me is not a new project but a

review of several previous journal papers done by experts. As the pandemic creating threat to all
 32

mankind; roaring across the globe I was not able to access laboratory facilities and other

facilities to develop own findings on this topic as State administration had imposed strict

regulations and institutes are closed from May itself.

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