THE

COMPETITION BETWEEN NITROGEN AND SULFUR DONORS FOR

COORDINATION ON THE SILVER(I) CATION

By

Taylor A. Murie

Submitted to

The Department of Chemistry, Lakehead University,

in Partial Fulfillment of the Requirements for the Degree of

Honours Bachelor of Science

Supervisor: Dr. C. D. MacKinnon

Department of Chemistry, Lakehead University

Thunder Bay, Ontario, Canada, P7B 5E1

April 2016

 Abstract

Progress has been made on the coordination of silver(I) to various 4,4-bithiazole (4-Tz)

ligands. 2,2-dimethyl-4-Tz as well as 2,2-diamino-4-Tz have been synthesized and

characterized using NMR and IR spectroscopy. Coordination to silver was attempted, however,

no crystals were observed although research is still ongoing in this area.

Computational DFT calculations were initiated in order to determine the theoretical

preferred coordination of silver(I) to 4-Tz. The rotational profile of 4-Tz has been determined

and it has allowed us to begin to optimize the lowest energy states of 4-Tz.

 Acknowledgements

First, I would like to thank my supervisor, Dr. Craig MacKinnon for showing me the world

of synthetic chemistry. This experience has been very eye-opening for me and has helped me

develop an appreciation for research. I consider myself lucky to have had the opportunity to

work with Dr. MacKinnon in his laboratory.

I would also like to thank my committee members Dr. Greg Spivak and Dr. Robert

Mawhinney for assisting me throughout this project. This project would not have been possible

without their help and guidance. Dr. Justin Jiang also assisted with this project on multiple

occasions and I would like to thank him for his assistance with various syntheses and

mechanisms.

I would also like to thank the MacKinnon lab members, Marnie Merchant and Joep

Trijbels. They have both been a great help in completing this project and it has been a pleasure

working with them.

The faculty and staff in the chemistry department also deserve a special mention as they

all played a part in the completion of this thesis throughout their assistance over the last four

years.

Lastly, I would like to thank my friends and family for their support and guidance.

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 Contents

Acknowledgements.........................................................................................................................i

Contents..........................................................................................................................................ii

List of Figures.................................................................................................................................iv

List of Tables...................................................................................................................................v

List of Schemes...............................................................................................................................vi

Abbreviations................................................................................................................................vii

1. Introduction..............................................................................................................................1

1.1. General Introduction to Coordination Chemistry..............................................................1

1.2. Bithiazole Coordination Complexes...................................................................................2

1.3. Potential Applications of Bithiazole Complexes................................................................4

1.4. Comparison to Other Inorganic Ligands............................................................................5

1.5. Synthetic Methodology.....................................................................................................5

1.6. Computational Chemistry..................................................................................................8

2. Research Intentions and Rationale...........................................................................................9

3. Experimental...........................................................................................................................10

3.1. General Considerations...................................................................................................10

3.2. Synthesis of 1,4-dibromo-2,3-butanedione.....................................................................11

3.3. Synthesis of 2,2-dimethyl-4-Tz.......................................................................................11

3.4. Synthesis of 2,2-diamino-4-Tz........................................................................................12

ii
4. Results and Discussion............................................................................................................13

4.1. Synthesis and Characterization of Brominated Diketones..............................................13

4.1.1. 1,4-dibromo-2,3-butanedione..............................................................................13

4.1.2. 1,4-dibromo-2,3-pentanedione............................................................................14

4.2. Synthesis and Characterization of the Variations of 4-Tz................................................14

4.2.1. 2,2-dimethyl-4-Tz.................................................................................................14

4.2.2. 2,2-diamino-4-Tz..................................................................................................16

4.3. Coordination to Silver(I) .................................................................................................16

4.4. Computational Calculations.............................................................................................17

4.5. Concluding Remarks. ......................................................................................................20

4.6. Future Work.....................................................................................................................21

5. References..............................................................................................................................23

6. Appendix A: Spectroscopic Data.............................................................................................24

1,4-dibromo-2,3-pentanedione 1H NMR spectrum..................................................24

2,2-diamino-4-Tz IR.................................................................................................24

iii
 List of Figures

Figure 1. Molecular structures of linear (A), bent (B) and off-axis linear (C) ligands.

Figure 2. Molecular structure of 2-Tz and 4-Tz.

Figure 3. The dihedral angle of 4-Tz, to be rotated about in the rotational profile analysis.

Figure 4. 1H NMR spectrum of 1,4-dibromo-2,3-butanedione obtained in CDCl3.

Figure 5. 1H NMR spectrum of 2,2-dimethyl-4-Tz obtained in CDCl3.

Figure 6. The PBE1PBE/6-31++G(d,p) rotational profile of 4-Tz.

Figure 7: The B3LYP/6-31++G(d,p) rotational profile of bipy.

iv
 List of Tables

Table 1. Amounts of ligand, metal salt and solvent used in silver(I) coordination attempts.

v
 List of Schemes

Scheme 1. The synthesis of 4-Tz.

Scheme 2. The mechanism of the formation of 4-Tz.

vi
 Abbreviations

bipy = 2,2-bipyridine

DNA = deoxyribonucleic acid

DFT = density functional theory

H = Hartree

hr = time in hours

IR = infrared

Me = methyl group

NMR = nuclear magnetic resonance

S = singlet

Tz = bithiazole

QTAIM = quantum theory of atoms in molecules

2-Tz = 2,2-bithiazole

4-Tz = 4,4-bithiazole

vii
1. Introduction

1.1 General Introduction to Coordination Chemistry

In coordination chemistry, crystal engineering refers to the attempt to generate

predictable solid state structures based on the preferred geometry of the ligand and metal

centre [1]. Transition metals with a d10 electron configuration, like silver(I), do not have a

preferred geometric structure, meaning they can coordinate in any configuration ranging from

linear to octahedral. d10 transition metals have full, spherically shaped outer shells. This leads to

no preferred ligand field stabilization energy, and therefore no preferred geometric structure.

When attempting to engineer a crystal structure, small changes like solvent, stoichiometry, or

counterions also need to be taken into account as they can have a large impact on the

geometric configuration of the resulting coordination compound. For example, changing the

stoichiometry of ligand to metal cation when crystal engineering with a d10 transition metal can

effectively change the crystal structure from a linear structure to a more complex one. As a

whole, our research group is particularly interested in heterocyclic ligands as the heteroatoms

compete for coordination sites in the corresponding crystal structure. This could lead to new

discoveries of applications of these ligands.

There are three possible conformations of planar cyclic bidentate ligands: linear, off axis

linear, and bent. Each conformation can lead to a different crystal structure [1].

1
In Figure 1, a linear ligand, 2,2-bipyridine (bipy) is shown. Linear ligands like compound A can

form coordination complexes ranging from linear to three dimensional diamondoid structures

[2]. Bent ligands exhibiting the same structure as compound B generally lead to chelation with a

metal, and therefore can lead to new and interesting crystal structures that have not been seen

before [1]. Compounds in an off axis linear configuration could potentially lead to extended

crystal structures, also making them interesting to investigate [1]. As a research group, we are

particularly interested in bent and off-axis linear bidentate cyclic ligands containing

heteroatoms.

A B C

Figure 1. Molecular structures of linear (A), bent (B) and off-axis linear (C) ligands.

1.2 Bithiazole Coordination Complexes

In bithiazole complexes, there are a number of ways coordination to a metal can occur.

Coordination can occur via an interaction at the sulfur group, chelation at the nitrogen groups

or coordination to a substituent present on the ring (R in Figure 2). Focus will be on 2,2-

bithiazole (2-Tz) and 4,4-bithiazole (4-Tz) as these isomers can lead to a chelation interaction.

Figure 2. Molecular structure of 2-Tz and 4-Tz.

2-Tz has been extensively researched by prior laboratory members in our group. Based

on the previous results of the coordination of 2-Tz with silver(I) from our lab and from others

work, we anticipate that the preferred interaction between 4-Tz and silver(I) will be chelation at

the nitrogen groups, potentially in addition to interaction with ring substituents (R), should such

substituents be present [3,4]. From the conjugation in the ring, it can be seen that there is only

one lone pair present on each nitrogen in contrast to each sulfur which has two lone pairs.

Based on the hybridization of the nitrogen, we anticipate that the lone pair will be planar and

lie within the plane of the compound. The sulfur is sp3 hybridized so we anticipate that the lone

pairs will lie above and below the plane of the compound [5]. With the sulfur lone pairs in this

configuration, it becomes difficult for a metal to form a strong chelation system as the angles

are not favourable. In comparison to the nitrogen, the sulfur is not a good donor, making a

chelation interaction more favourable at the nitrogen groups. Although Tz contains the

unfavourable donor sulfur groups, these compounds have the ability to chelate due to the ring

conjugation, unlike other non-sulfur containing compounds like bipyrrole.

3
1.3 Potential Applications of Bithiazole Complexes

Bithiazole compounds have many potential applications, including as anticancer

complexes, soft magnetic metals and polymers [6]. Bleomycin is an anticancer drug that has

bithiazole in the active portion of the compound. The bithiazole moiety binds to the DNA of

malignant cells via intercalation, and effectively inhibits further synthesis and replication

[6,7,8]. Bithiazole derivatives have also found application as soft ferromagnets [8].

As a ligand in coordination and organometallic chemistry, bithiazole can be compared to

one of the most widely utilized inorganic ligands, bipy. Due to the difference in bite angle

between 4-Tz and bipy, 4-Tz may have a greater selectivity for specific metals. In the literature,

bithiazole complexes are usually coordinated with larger or heavier (late) metals [6,8,9]. For

reactions where bite angle is not an issue, bipy and 4-Tz may be able to be used

interchangeably. 2-Tz has shown to have selectivity towards larger and heavier metals at least

in the set of Group 10 d10 transition metals, and we anticipate that 4-Tz will demonstrate this

same characteristic. If this is the case, there is potential for these compounds to be used in

situations that need to test for (sense) or remove heavy metals from a material, like drinking

water, adding another potential application of these compounds.

4
1.4 Comparison to Other Inorganic Ligands

4-Tz can be compared to other chelating ligands, namely the ubiquitous inorganic ligand

bipy. The two complexes share a few similar characteristics. 4-Tz can also be compared to its

geometric isomer, 2-Tz.

First, to compare to bipy, both ligands have the capability of chelating and acting as a

bidentate ligand. Bipys primary mode of coordination is via a chelation interaction, which is

also what we anticipate to see for 4-Tz [10].

Comparing the regioisomers 2-Tz and 4-Tz, they display many of the same superficial

characteristics. The difference between the two isomers is the placement of the sulfur groups

within the ring system. This placement has a large impact on the sterics of the compound. The

location of the sulfurs in 2-Tz are sites that could potentially be substituted in 4-Tz. Substituting

with a large R group at those sites (5 and 5 in 4-Tz) would be quite challenging in comparison to

substituting 2-Tz at its open sites. This steric hindrance in the 5 and 5 sites drastically

changes the sterics of this ligand and could lead to new crystal structures with greater porosity

than what we have seen with 2-Tz.

1.5 Synthetic Methodology

Having different substituents can cause a change in the electronics and sterics of a

ligand, which would allow for new potential bonding pockets and/or differences in electron

richness. Previous members of our group have worked on derivatives of the ligand 2-Tz,

5
however, no one in our group has looked at the geometric isomer 4-Tz. Both are made by a

double ring closing reaction, but it is much easier to generate asymmetrically substituted 4-Tz.

In the synthesis of 4-Tz, when using an asymmetric diketone, the product would selectively be

the asymmetrically substituted 4-Tz. In the synthesis of 2-Tz, on the other hand, two

equivalents of a monoketone are used. Hence, two different ketones, R1(CO)CH2Br and

R2(CO)CH2Br, would have to be added to the reaction mixture to obtain an asymmetric product,

which would then necessitate separation as there would be a mixture of products, R1R12-Tz,

R1R22-Tz, and R2R22-Tz. The ease with which an asymmetric species is made is clearly seen

when looking at the reaction scheme and mechanism.

Scheme 1. The synthesis of 4-Tz.

As can be seen in the mechanism in Scheme 2, the sulfur group from the thio complex C

has a zwitterionic resonance structure. The existence of this resonance structure allows attack

from the sulfur to the carbon alpha to the ketone. Bromine departs, combining with a proton

lost from the amino group of the thio complex, producing hydrobromic acid as a by-product. In

6
the next step, the intramolecular ring closing occurs via attack of the nitrogen lone pair at the

carbon of the ketone, pushing electron density towards the oxygen, forming a zwitterionic

complex. Next, a tautomerization occurs, moving the hydrogen from the nitrogen to the oxygen

to balance out the charges. A hydroxyl group and a proton eliminate producing conjugation in

the ring with the loss of a water molecule. This leaves behind half of 1,4-dibromo-2,3-

butanedione. The mechanism repeats again in a stepwise fashion to form the other ring.

Previous work done showed the isolation of a single ring species, demonstrating that this

reaction occurs in a stepwise fashion [11].

Scheme 2. The mechanism of the formation of 4-Tz.

7
1.6 Computational Chemistry

Two programs, Gaussian and AimALL, will be used in order to perform the

computational DFT calculations for this project. The aim of the computational work is to

provide insight on the electron density around each heteroatom in various substitutions of 4-Tz

in addition to the bite angle of the nitrogen groups.

The first step in this process is to determine the rotational profile of each variation of 4-

Tz in order to determine the lowest energy conformation of the ligand about a predefined

angle. This will be done using Gaussian.

Figure 3. The dihedral angle of 4-Tz, to be rotated about in the rotational profile analysis,

shown here in the defined 0 degree orientation.

Based on the analysis of the rotational profile, a geometry optimization and computation of

force constants and the resulting vibrational frequencies can then be run on the lowest energy

state(s). The rotational profile can also help determine the amount of energy required to form a

certain conformation of a compound. The optimized lowest energy conformation(s) can then be

transferred into AimAll, where the electron density can be determined at each atom within a

molecule and the bite angle of the dihedral angle can be calculated. From this information, it

8
can be determined where the bonding of a specific ligand is preferred to occur to a metal as

well as whether or not there is specificity for chelation with heavier or larger metals.

2. Research Intentions and Rationale

The intent of this research project was to determine the bonding capabilities of 4-Tz to

silver(I) and to compare with known 2-Tz ligands previously investigated in our laboratory. This

was to be done through two parts: laboratory work and computational chemistry.

For the laboratory work, the goal was to synthesize variations of 4-Tz, coordinate them

to silver(I) and isolate the crystals. The next step of the laboratory work was to obtain a crystal

structure of the coordination complex. The computational portion was to perform an analysis

of each substituted 4-Tz (synthesized in the laboratory portion) to determine the theoretical

results for the locations of the electron density and lone pairs of each heteroatom present in 4-

Tz. This would lead to the calculation of the bite angle of the chelating nitrogen groups and

allow comparison to bipy. It could also allow for determination of the selectivity of 4-Tz towards

larger and heavier metals.

These two related goals would allow for the determination of the electronic structure

and relative donor abilities of the lone pairs of 4-Tz, which can be compared to 2-Tz.

Comparison of the computational results with the synthetic results will be evaluated to validate

(or improve) the computational method used.

The rationale behind this project leads back to crystal engineering. These heterocyclic

ligands are of interest to us as they create competition for coordination sites in the

9
corresponding crystal structures. This could lead to discoveries of new applications for such

ligands.

3. Experimental

3.1 General Considerations

The reactions used in the preparation of the ligands were performed under an inert

atmosphere of N2 unless otherwise stated. All of the reagents used for the syntheses were of

analytical grade and were used as received from Aldrich without further purification. NMR

spectra were recorded on a Varian Unity Inova 500 MHz spectrometer at 499.99 MHz for 1H.

Chemical shifts are reported in ppm relative to the internal standard of TMS. IR spectra

obtained using a Nicolet 380 spectrometer.

3.1.1 Computational Considerations

Computational results were obtained with Gaussian Suite 03 [12] using the PBE1PBE

hybrid density functional and the 6-31++G(d,p) basis set [13,14]. Gaussian Suite was used to

complete DFT calculations and AimALL will be used to complete electron density analysis [15].

AimAll allows users to perform an analysis on individual atoms within a molecule, and

10
determine electron density on and around those atoms. AimALL is based on the QTAIM,

formulated by Bader [15].

Using Gaussian, the initial attempts to calculate the rotational profile for unsubstituted

4-Tz were not converging and the application was failing. It was then decided that we would

run the calculations at stationary angles using 10o increments instead of running the entire

calculation at once.

3.2 Synthesis of 1,4-dibromo-2,3-butanedione

A solution of 2,3-butanedione (2.84 g, 32.99 mmol) in chloroform (8 mL) was added

slowly from a dropping funnel into a solution of Br2 (10.55g, 66.02 mmol) in chloroform (4 mL)

at room temperature. Once the addition was finished, the mixture was heated to 48oC and

allowed to stir over 3 hrs. The mixture was then placed into an ice bath for approximately 2 hrs

and then the light yellow precipitate was filtered. The yield for this reaction was 32%. 1H NMR

(499.9 MHz, CDCl3): 4.34 (s, 4H, CH2) [16].

3.3 Synthesis of 2,2-dimethyl-4-Tz

1,4-dibromo-2,3-butanedione (0.5 g, 2.05 mmol) and thioacetamide (0.31 g, 4.10 mmol)

were dissolved in dry methanol (10 mL). The mixture was then allowed to reflux for 3 hrs. The

resulting solution was added to approximately 100 mL of H2O and then neutralized using

11
aqueous Na2CO3. Excess solvent was removed using a rotary evaporator and the precipitate

filtered to yield a light yellow-brown solid. The yield for this reaction was 86%. 1H NMR (499.9

MHz, CDCl3): 3.76 (s, 6H, CH3), 7.58 (s, 2H, Tz) [7].

3.4 Synthesis of 2,2-diamino-4-Tz

1,4-dibromo-2,3-butanedione (0.5 g, 2.05 mmol) and thiourea (0.313 g, 4.10 mmol)

were added to ethanol (20 mL). The resultant mixture was allowed to reflux in air under

atmospheric conditions for 6 hrs. It was then poured into approximately 40 mL of H2O and

neutralized using aqueous NH4OH. The white, crystalline solid was then filtered. The yield for

this reaction was 57%. IR: 3446, 3296, 3153, 3127, 1596, 1522, 1298, 1025, 773, 704 cm-1 [17].

12
4. Results and Discussion

4.1 Synthesis and Characterization of Brominated Diketones

4.1.1 1,4-dibromo-2,3-butanedione

This synthesis was based on a literature preparation using acetic acid and urea for the

bromination of a monoketone (2-octanone), however the NMR spectrum of the product from

this reaction was not promising [18]. Another literature preparation of this precursor was found

and the reaction worked well, this time using CHCl3 as the solvent [16]. The 1H NMR spectrum is

simple, and displays a single peak at 4.345 ppm.

Figure 4. 1H NMR spectrum of 1,4-dibromo-2,3-butanedione in CDCl3.

13


The large peak at 4.34 ppm corresponds to all four protons present in this compound. This

precursor could then be used to create symmetric variations of 4-Tz.

4.1.2. 1,4-dibromo-2,3-pentanedione

The purpose of this reaction was a proof of concept reaction demonstrating the

asymmetric substitution of 4-Tz. Unfortunately, this reaction was unsuccessful in the initial

bromination step. The bromination of pentanedione was completed using the same procedure

as was done for the butanedione [16]. The NMR spectrum showed no significant peaks

demonstrating that a bromination had taken place and therefore the reaction was deemed

unsuccessful. In the future, this reaction could be attempted using another solvent,

brominating agent, or possibly be allowed to heat for a longer period of time to allow the

reaction to occur.

4.2 Synthesis and Characterization of the Variations of 4-Tz

4.2.1 2,2-dimethyl-4-Tz

The synthesis of methyl substituted 4-Tz was one of our most successful reactions. This

synthesis utilized the previously synthesized brominated butanedione and was a very

14
straightforward reaction. This reaction was taken from a literature preparation [7]. The product

precipitated out of solution readily and the 1H NMR spectrum was easy to characterize.

Figure 5. 1H NMR spectrum of 2,2-dimethyl-4-Tz obtained in CDCl3.

The larger peak at 3.76 ppm integrated for all six protons from the two methyl groups on the 4-

Tz and the other peak at 7.58 ppm integrated for two protons, and were in the aromatic range

indicating the protons directly substituted on the bithiazole. These peaks corresponded to

literature values for this complex [7].

15
4.2.2 2,2-diamino-4-Tz

This synthesis was based on a literature preparation [18]. An IR spectrum of this

compound was acquired in order to compare it with the paper. All peaks matched between the

two papers, and therefore it could be concluded that the synthesis was successful.

4.3 Coordination to Silver(I)

An initial trial was run in order to see if there would be any interaction between a

silver(I) salt and 2,2-dimethyl-4-Tz. This was done using small masses of AgNO3 and 2,2-

dimethyl-4-Tz in benzene. A white solid was produced in this reaction.

Three attempts were made to coordinate the 2,2-dimethyl-4-Tz to silver(I) using varying

amounts of ligand, metal and solvent. The three silver compounds that were used in this

endeavor were AgBF4, AgPF6 and AgClO4; these salts were chosen based on successes

previously noted for generating crystalline coordination compounds.

Table 1. Amounts of ligand, metal salt and solvent used in silver(I) coordination attempts.


Metal Salt Mass of Salt (mg) Mass of Ligand (mg) Solvent Volume (mL)

AgClO4 42.3 20.1 15

AgPF6 51.6 20.2 20

AgBF4 39.7 19.9 16

16
Each reaction vessel tube was filled with the masses and volumes of the metal salt, ligand and

solvent as shown in Table 1. These tubes were then placed under vacuum and frozen by placing

the tube in a liquid nitrogen bath. Once frozen, the tubes were sealed under vacuum. These

tubes were then placed in an oven overnight at 100oC. The reaction conditions and

temperatures used for this reaction were identical to those used for successful coordination of

2-Tz, however, these same conditions did not work for 4-Tz. Black precipitate was formed when

heated for all three attempts, which is characteristic of a silver precipitate rather than

coordination. In the future, other stoichiometric ratios and solvents could be used in order to

promote coordination, and therefore obtain a crystal which can be analyzed.

4.4 Computational Calculations

The first step of the computational calculations was to perform a rotational profile

analysis of the unsubstituted 4-Tz as well as the methyl substituted, amino substituted and

asymmetrically trimethyl substituted 4-Tz compounds. Research is still ongoing in this area as

only the unsubstituted 4-Tz rotational profile has been successful at this point.

17
 Rotational Profile of 4-Tz

-1136.23

-1136.232
Energy (Hartrees)

-1136.234

-1136.236

-1136.238

-1136.24

-1136.242

-1136.244
0 20 40 60 80 100 120 140 160 180 200
Dihedral Angle (degrees)

Figure 6. The PBE1PBE/6-31++G(d,p) rotational profile of 4-Tz.

This rotational profile demonstrates two energy barriers and two minima, indicating

that there are two points of rotation where the compound is most stable. The two minima

correspond to approximately 35o and 180o, meaning that the conformation with the nitrogen

groups trans to one another is very stable, as well as a conformation where the molecule is

slightly off-planar. This 35o minimum is likely due to the steric hindrance at the 5 and 5 sites of

the 4-Tz.

As can be seen in Figure 7, bipy has a very similar rotational profile to 4-Tz. It is

important to note that the rotational profile of bipy seems to be a mirror image of that of 4-Tz,

however this is because the Ramana Rao research group determined the rotational profile had

opposite dihedral angle starting points than we did (i.e. our 0o conformation was their 180o

conformation and vice versa) [19].

18


Figure 7: The B3LYP/6-31++G(d,p) rotational profile of bipy.




Because of the synthetic methodology of 4-Tz, the 2 and 2, and 5 and 5 sites can be

readily substituted with various R groups. For the rotational profile calculations thus far, all R

groups are hydrogens. The 5 and 5 sites are very sterically hindered sites in 4-Tz. Even having

just hydrogen in the 5 and 5 sites affects the rotational profile, indicating that even hydrogen

groups are large enough to create a steric barrier to rotation, as seen by the local maximum at

0o in Figure 6. Bipy also has hydrogens in the same relative positions as 4-Tz. This leads to very

similar rotational profile, where the cis conformation is again a local maximum.

Further work could include performing analyses of the rotational profiles of substituted

4-Tz compounds as well as substituted 2-Tz compounds and comparing the differences. The

optimization and frequency calculations for each minimum would need to be run for each

variation of Tz. These optimized compounds can then be transferred into AimALL to perform an

19
analysis on the electron density and lone pairs at the heteroatoms in the ring system. This

would lead to a true comparison of the computational work to a coordination complex.

4.5 Concluding Remarks

In conclusion, the synthesis of the precursor brominated diketone for symmetrically

substituted 4-Tz was successful, as determined by 1H NMR spectroscopy. The 1,4-dibromo-2,3-

butanedione was then used to synthesize successfully the methyl substituted 4-Tz as well as the

amino substituted 4-Tz. The 1H NMR spectrum for the methyl substituted 4-Tz demonstrated

that the synthesis was successful and the IR for the amino substituted 4-Tz also showed that

the reaction yielded the correct product.

In summary of the laboratory work, two 4-Tz ligands have been synthesized, namely

2,2-dimethyl-4-Tz and 2,2-diamino-4-Tz. Both were created using the synthesized precursor

1,4-dibromo-2,3-butanedione. Characterization was by 1H NMR spectrum for the methyl

substituted 4-Tz and IR for the amino substituted 4-Tz.

In terms of computational work, the rotational profile for 4-Tz was found through the

use of Gaussian Suite 03. It could then be compared to other ligands, like 2-Tz and bipy. This

comparison demonstrated a steric barrier to rotation present in 4-Tz that we do not expect to

be present in 2-Tz due to lack of steric hindrance, but that is present in bipy. This information is

useful when making inferences on bonding patterns of these ligands.

20
4.6 Future Work

Future work could include synthesizing more variations of 4-Tz, including ones that have

different substituents in the 5 and 5 positions of the compound. Finding a general synthesis to

dibromoketones that would allow synthesis of a variety of different substituents on 4-Tz would

also be beneficial.

Attempting to coordinate the different variations of 4-Tz to silver(I) again would be a

part of the future work as well, making modifications to the previously attempted

stoichiometric ratios of ligand to metal and changing the solvent or reaction temperature.

Through trial and error, we anticipate that it should be possible to obtain crystals of the

coordination complex, which could then be analyzed using x-ray crystallography.

In terms of the computational work, building other variations of 4-Tz and running a

rotational profile analysis on them would be beneficial to compare to unsubstituted 4-Tz. In

addition, completing the optimization and frequency calculations for each variation of 4-Tz

would also be required in order to transfer the lower energy states of these compounds into

AimALL. A QTAIM analysis using AimALL would also need to be done in order to determine the

electron density around each heteroatom and to determine the location of the lone pairs of the

sulfur and nitrogen on 4-Tz. This would lead to an accurate determination of the bonding mode

of 4-Tz to the metal that could then be compared to work in the laboratory.

Once the above work is completed, these complexes could then be tested for their

selectivity for larger and heavier metals and the bite angle of each variation could also be

determined. Depending on their selectivity, this could open up new applications of these

21
complexes to sense for, or even potentially remove larger or heavier metals in substances

where they need to be monitored, like water.

This is just a small indication of where this work could take these compounds. Future

research will be required to determine the potential of these ligands for other applications.

22
5. References

1. C.D. MacKinnon, S.L.M. Parent, R.C. Mawhinney, A. Assoud, and C.M. Robertson.,
CrystEngComm 2009, 11, 160.
2. G. B. Gardner, D. Venkataraman, J. S. Moore and S. Lee, Nature, 1995, 374, 792.
3. B.-L. Chen, K.-F. Mok and S.-C. Ng, J. Chem. Soc., Dalton Trans., 1998, 4035.
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6. Appendix A: Spectroscopic Data

1,4-dibromo-2,3-pentanedione 1H NMR spectrum in CDCl3

2,2-diamino-4-Tz IR

24