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. T .‘I‘. "25;:

ABSTRACT

THE KINETICS AND MECHANISMS OF THE FORMATION OF METAL COMPLEXES

CONTAINING NON-CYCLIC AND MACROCYCLIC LIGANDS

By

Karim Nafisi-Movaghar

In this project the reaction of [a,a'"-[i50pr0py1idenbis
(azo)]di-astibenendato]nickel(II), (NiMMK) with ethylinediamine and
1,3 - prOpanediamine has been investigated in the presence of solvent.
NiMMK contains a ligand with cis-oriented CO groups. The reaction of
ethylenediamine with NiMMK results in the formation of macrocyclic
complex with four nitrogen donors, [3,3,9-trimethyl-6,7,12,13
tetraphenyl-l,2,4,S,8,ll-hexaazacyclotrideca-l,4,6,12-tetraenato]
nickel(II), (NiMcyclo-IS). With 1,3-pr0panediamine, however, only
one of the CO groups of NiMMK undergoes condensation producing a complex
with a non-cyclic ligand, [a'[[1-[[2-[(Seamin0pr0pyl)amino]-l,2-
diphenylviny1]azo]-1-methylethyl]azo]-a-stibenolato]nickel(II),
(NiApSo).

The reactions were followed spectrOphotometrically in
tetrahydrofuran. The formation of NiApSo is found to involve a
single slow step, but the formation of NiMcyclo-13 involves two slow
steps (XVI). It was also found that the reactions of amines with
NiMMK are base catalysed. Kinetics data have been obtained for the
reactions. The dependence of the rate of the reactions on the

hydroxide concentration and each of the reactants has been

€60

(:7 investigated. A mechanism consistent with all the experimental data

is prOposed.

THE KINETICS AND MECHANISMS OF THE FORMATION OF METAL COMPLEXES

CONTAINING NON-CYCLIC AND MACROCYCLIC LIGANDS

By

Karim Nafisi-Movaghar

A THESIS

Submitted to
Michigan State University
in partial fulfillment of the requirements

for the degree of

MASTER OF SCIENCE

Department of Chemistry

1974

To Terry and Jabbar

ii

AC KNOW LL‘DGMENTS

The author would like to thank Dr. Gordon A. Nelson for his
expert and imaginative professional guidance, his understanding, and
his sincere friendship throughout the course of this study.

The author wishes to express his gratitude to the Department
of Chemistry, Michigan State University, for the financial aid paid to
me as a graduate Teaching Assistnat. Thanks also goes to all my fellow
graduate students for their very useful discussions.

Finally, for the inspiration that has made the agony of

this graduate student more than worthwhile, I thank Terry.

iii

TABLE OF CONTENTS

CHAPTER ONE: Introduction .

CHAPTER TWO: Experimental . . . . . . . . . . . . . .

1.

2.

3.

Preparation of Materials .
A. Nickel Complexes .

B. Amines .

C. Solvents .

D. Sodium Hydroxide .
Physical Measurements

General Procedure for Obtaining Kinetics Data

CHAPTER THREE: Kinetics and Data Treatment

1.

The Kinetics of the Reactions of NiMMK with

1,3 PrOpanediamine .

A. 1,3-Propanediamine Dependence of the Rate

B. NiMMK Dependence of the Rate .

C. Sodium Hydroxide Dependence of the Rate
Kinetics of the Reaction of NiMMK with
Ethylenediamine

A. Ethylenediamine Dependence of the Reaction Rate
B. NiMMK Dependence of the Reaction Rate

C. Sodium Hydroxide Dependence of the

Reaction Rate

CHAPTER FOUR: Mechanism of the Reactions

Benzoyl Derivative of the Intermediate .

iv

10

10

10

10

10

ll

11

ll

13

13

29

4O

4O

47

SS

57

CHAPTER FIVE:

APPENDIX .

BIBLIOGRAPHY .

Suggestions for Future Work .

. 64

. 68

. 83

LIST OF TABLES

TABLE I: A Set of Kinetics Data for the Reaction
between NiMMK and 1,3—Propanediamine .

TABLE II: 1,3-Propanediamine Dependence of the Rate .

TABLE III: NiMMK Dependence of the Rate .
TABLE IV: Sodium Hydroxide Dependence of the Rate .
TABLE V: A Set of Kinetics Data of the Reaction

of NiMMK with Ethylenediamine
TABLE VI: [Ethylenediamine] Dependence of the

First and Second Steps

TABLE VII: [NiMMK] Dependence of the First and Second Step
TABLE VIII: [Sodium Hydroxide] Dependence of the

First and Second Step
TABLE IX: Mass Spectrum of NiApSo .

vi

. 31

. 41

. 42

. 48

. 59

FIGURE

FIGURE

FIGURE

FIGURE

FIGURE

FIGURE

FIGURE

FIGURE

FIGURE

FIGURE

11:

III:

IV:

VI:

VII:

LIST OF FIGURES

Absorption Spectrum for Reaction of NiMMK
with 1,3-Pr0panediamine . . . . .
Absorption Spectrum of Equal Concentrations
of NiMMK,(a) and NiApSo,(b)
A Computer Plot of Absorbance vs. Time
of the Reaction between NiMMK and
1,3-Propanediamine . . .

A Plot of k0 vs. 1,3—Propanediamine

bs

Concentration for the Reaction between
NiMMK and 1,3-Pr0panediamine

A Plot of k0 vs. Sodium Hydroxide Concentration

bs

for the Reaction between NiMMK and 1,3—Propanediamine .

Absorption Spectrum of the Reaction of
NiMMK with Ethylenediamine
Absorption Spectrum of Equal Concentrations

of NiMMK(a) and NiMcyclo-13(b)

VIII: A Computer Plot of Absorbance vs. Time

IX:

for the First Step of the Reaction of
NiMMK and Ethylenediamine .

A Computer Plot of Absrobance vs. Time
for the Second Step of the Reaction of
NiMMK and Ethylenediamine .
Ethylenediamine Dependence of the Rate

of the First Step

vii

15

. 20

. 23

. 27

. 32

. 34

. 36

. 38

. 43

FIGURE

FIGURE

FIGURE

FIGURE

FIGURE

FIGURE

FIGURE

FIGURE

FIGURE

FIGURE

XI:

XII:

XIII:

XIV:

XV:

XVI:

XVII:

Ethylenediamine Dependence of the Rate

of the Second Step . . . . . . . . . . . . . . .
Sodium Hydroxide Dependence of the Rate

for the Second Step .
Sodium Hydroxide Dependence of the

First Step for the Reaction between

NiMMK and Ethylenediamine

Sodium Hydroxide Dependence of the Second Step

for the Reaction between NiMMK and Ethylenediamine .

Absorption Spectrum for Reaction of NiMMK
with 1,2-Propanediamine
Absorption Spectrum for Reactions of NiDMK
with Ethylenediamine .
[NiMMK] Dependence for the Reaction between

1,3-Propanediamine and NiMMK .

XVIII: [Sodium Hydroxide] Dependence for the

XIX:

XX:

First Step of the Reaction between
NiMMK and Ethylenediamine .

[NiMMK] Dependence for the Second Stage of the
Reaction between NiMMK and Ethylenediamine .
[Sodium Hydroxide] Dependence for the Reaction

between NiMMK and 1,3-Pr0panediamine .

viii

. 45

. 49

. 51

. 53

- 64

. 66

- 69

- 7O

- 71

. 72

CHAPTER ONE

INTRODUCTION

The ability of transition metal ions to direct the steric
course of certain condensation reactions between organic molecules has
been recognized for several years. Many of the products of these
condensation reactions are natural products, for example, derivatives
of porphin or corrin ring systems.

During the past ten years or so there has been considerable
interest in the use of transition metal ions for the synthesis of
compounds containing macrocyclic ligands which may serve as models for
biological processes which are known to require the presence of
metal ions. Research into the synthesis and characterization of
complexes containing macrocyclic ligands has been extensive, and
several reviews which summarize the research in the area have been
published1-6. The most extensively studied systems are those which
lead to the formation of complexes containing macrocyclic ligands
with four nitrogen donors. Condensation reactions between carbonyl
compounds and primary amines have been extensively employed for the
formation of these new macrocyclic ligands. The groups of Busch and
Curtis have been particularly active in this area (see reference 5)
although significant contributions have been made by other workers
including Jager7'10, Blackll, Cumming512-14, Green and Taskerls, and
Bamfield16, Recently Kerwin and Melson reported some reactions
between amines and ligands derived from hydrazonesl7. The research

group of Helm has carried out extensive studies of the synthesis,

characterization and reactions of complexes of this type, although

their syntheses have been accomplished by direct reaction between the
free organic macrocycle and the metal ion rather than by "in situ"
reactions which are governed more directly by template effect518_20.
While recognizing the significant results of Holm's research, we shall
concentrate this discussion on "in situ" process; i.e., those

processes in which the reactants are brought together by coordination

to the same metal ion. The proximity of the reactive sites then

promotes a reaction that would take place much less readily, if at

all, in the absence of the metal ion.

In spite of the wealth of data on the synthesis and characteriza-
tion of metal complexes containing macrocyclic ligands with nitrogen
donors, there is little information on the factors that are important
in controlling the reactions or on the role that the metal ion plays
in the "in situ" condensations. Indeed Lindoy and Busch in their
article5 concerning complexes of macrocyclic ligands comment:

Unfortunately the principles underlying some

of the synthetic procedures are yet little understood,

and in addition to its contribution to fundamental

understanding, the elucidation of the mechanisms of

the formation of macrocyclic complexes will undoubtedly

be of great benefit in the design of new syntheses.

Metal-ion control in the synthesis of Schiff base complexes
has been the subject of a recent review21 although reactions of
salicylaldehyde complexes with amines have been discussed earlierzz’zs.
The nature of both the metal ion and the ligand is an important
criterion to be considered in planning the synthesis of a Schiff
base complex. Nunez and Eichhorn24 reported one of the early studies
on the kinetics of formation of metal complexes containing Schiff

bases. The reactions of nickel(II) and copper(II) with salicylal-

dehyde and glycine were investigated and it was found that the nature

of participation of the metal ion in Schiff base formation is
dependent on the metal ion and on the order of mixing of the reactants.
The proposed mechanism involves the formation of an intermediate, I,

followed by reaction to produce the Schiff base complex, II.

C NH2‘
0“ HC’NC2V \ |./ CH2
+2I —--' x'I‘x 3;
CH0 c /|\ cao o’ ‘o

I, \o
0 I
o l/
\Ni—O

Leussing and co-workers25 have studied the formation of Schiff bases
in the presence of metal ions in aqueous media, and the effects of
metal ions on the rates of formation have been discussed26. Recently,
Curti527’28 proposed the following mechanism for reactions between

metal-amine complexes and carbonyl compounds:

NH M9 M0 Me Me C 2 Me
\:3+ \ / \C:_/ \C/
/ I u ' n u
NH2 N O
\ 2
Ni +
/ +
NH2 H
AAe 5A9
‘\\(>’,K:IE%:’,/
Me I 3,
NH
\ 02+
I
/
h"12

With the exception of the above work of Curtis and the report on the
stepwise formation of phthalocyaninezg, no detailed studies related
to the formation of complexes containing macrocyclic ligands with
nitrogen donors have been reported.

In 1968, Blinn and Busch described the only study of the
kinetics of macrocycle formationso. This involved the reaction between
2,3 pentanedione-bis (mercaptoethylimino) nicke1(II) and a,a'-
dibromo-o-xylene. The "kinetic coordination template effect" was
demonstrated by following the reaction spectrOphotometrically in
dichloroethane at 25°. A two-step mechanism was proposed; the first

being slow, (III,IV) and the second ring closure step (IV-V) very rapid.

f—fi /___\
3\C/ \ / BrCH CH3\ / \I /
1c Ni 4' C, I | Ni CH
01/ \N/ \5 BrCHz CH/C\\N/Ilr’ Is 2
3 \ / 3

Since this report, other studies of reactions of the mercaptide function

of complexes containing mercaptoamines with alkyl and aryl halides

1-34

have been reported3 although no further studies of macrocycle

formation have appeared in the literature.

Reactions between some monohydrazones, VI and ketones,

3 4
R R C=0 in the presence of nickel (II) ions have been reported

recently by Melson and et al.

1 2
VI = =
a,R R C6H5

R] 2 VI b,Rl=R2=CH3
R
c... c VI C,R1=C(CH3)3,R2=H

VI

In all cases, nickel(II) complexes which contain ligands

 

 

derived from two monohydrazones and one ketone, VII, are obtained35—37.
2..
F ]
RL\ R2
1’ 1- 2_
C = C VII a,R —R ‘CGHS
/' \. ___ 3 l_ 2_
O N N\ /R VII b,R -R -013
/C\ 4 VII c,R1=C(CH3)3,R2=H
() P4===f4 R
\ /
C::==:€i
l/’
R R2
VII J

In the absence of nickel (II) ions, VIII is obtained.

1 2
R R
\ /
C—C
47 It
0 N.N=CR3R4
VIII.

Thus the nickel (II) ions control the condensation reactions with the
result that products are formed which are not obtained in the absence

of the metal ions. The mode of coordination of the ligands with

3 4 2 2

R = R = CH and R1 = R = CH3 (VIIb) and R1 = C(CH3)3, R = H,

3!
(VIIC) has been established from 1H nmr spectra38 and it is assumed
that ligands derived from (VIIa) coordinate in a similar manner, as

in IX.

N

ON \\/CH,
0/ 2%
L E

"/ \c/

The reactivity of the coordinated CO groups of these ligands towards
amines has been investigated. Since they are oriented in a cis
configuration in the nickel complex, reaction with a suitable diamine
would be expected to result in a complex with a macrocyclic ligand
containing four nitrogen donors. In the presence of diamines, the
Species X have been obtained17. The mode of coordination and
conformation of the new chelate ring has been established from 1H nmr

and circular dichroism spectra39

R1 R2
\C_ C /
/ \
/N N\ x a,R1=R2=C6H5,R5=H
R—CH / N 1 2 5
| Ni \/CH3 x b,R =12 =C6H5,R =CH3
CH2 / \ /C\ 1_ 2_ s_
\N- N CH3 x c,R -R —CH3,R 41

With 1,3 diaminOprOpane, replacement of only one of the coordinated
oxygens occursl7, producing a complex containing a non-cyclic,

potentially pentadentate ligand XI.

N

H
C/

R2I

3

R' R2
\ __C/
HN—(CH2)3 \ /C \N
2 N\N / \N
/N \C/CH3 R1=R2=C6HS
C) \\\\ ””' \\‘(:Fl
C

R/

/

It is interesting to note that the complex with ligand VIIC does not
react with diamines, even under forcing condition537. Obviously the
nature of the group attached to the coordinated CD has a marked
influence on the reactivity of the carbonyl.

It is appropriate at this time to determine the mechanisms of
reactions which lead to the formation of complexes containing macro-
cyclic ligands. This dissertation is a report on the kinetics and
mechanism of ring closure reactions between IX, R1 = R2 = C6HS
and some diamines such as ethylenediamine, 1,2-propanediamine and 1,3-
pr0panediamine in solution. (The preparative reactions were carried
out in the absence of solvent). It is anticipated that this study
should lead to a more complete understanding of the mechanism of

macrocycle formation and may lead to the development of new and

more effective synthetic procedures.

CHAPTER TWO

EXPERIMENTAL

1. Preparation of Materials

 

A. Nickel Complexes

 

[a,a"'[IsoprOpylidenbis(azo)di~a stibenendato]nickel(ll),
(NiMMK), [3,3-Dimethyl-6,7,12,lS-tetraphenyl-l,2,4,5,9,ll-hexaazacylo-
trideca-l,4,6,12-tetraenato] nickel(II), (NiHcyclo-13), [3,3,9-
Trimethyl-6,7,12,13 tetraphenyl-12,4,S,8,ll-hexaazacyclotrideca-
1,4,6,12-tetraenato] nickel(II), (NiMcyclo-IS) and [a'[[l-[[2-
[(S-AminOprOpyl)amino]-l,2-diphenylvinyl]azo]-1-methylethyl]azo]-
a-stibenolato] nickel(II), (NiApSo) were prepared as previously
described32-34. NiMMK, NiHcyc1013 and NiMcyc1013 were recrystalyzed

from acetone and NiApSo was recrystalyzed from tetrahydrofuran.

B. Amines

 

Ethylenediamine, 1,2-propanediamine and 1,3-propanediamine
were distilled from sodium hydroxide under nitrogen, collected over

sodium hydroxide and stored in a dry box.

C. Solvents

 

l. Tetrahydrofuran (Mallinckrodt) was refluxed and
distilled from sodium to remove water, benz0phenone was added as an
indicator. (Water content of the solvent after distillation was 60 ul per m1).

2. Acetonitrile (Baker analyzed reagent) was refluxed and
then distilled from calcium hydride. Other solvents used were dichloro-

ethane, dimethyl sulfoxide, dimethylformamide, dioxane and pyridine.

10

11

They were all reagent grade or equivalent and used as supplied.

D. Sodium Hydroxide

 

Stock solutions of sodium hydroxide were prepared by

dissolving solid sodium hydroxide in absolute ethanol, and standardized
with a standard solution of potassium hydrogen phthalate (Fisher
scientific Company) using either phenolphtalein¢xr pH meter for deter-
mination of end point.

Note: All other chemicals used were reagent grade or

equivalent.

2. Physical Measurements

 

All visible and ultraviolet spectra were obtained between
600-275 nm by use of a Unicam SP800 B spectrophotometer. Kinetics
data were obtained from a Beckman model Du spectrOphotometer. Both
Unicam and Beckman spectrOphotometers were calibrated for absorption
with a standard solution of potassiumdichromate in sulfuric acid and
for wavelength with a didymium filter. The base lines of the Spectra
were obtained via air vs. air.

Mass spectra were determined with a Hitachi-Perkin-Elmer
RMU-60 mass spectrometer. A pH meter model LS S-30005 (Sargent) was

used for preparation of the standard sodium hydroxide solution.

3. General Procedure for Obtaining Kinetics Data

 

A weighed amount of MiMMK was dissolved in a known quantity

3

of tetrahydrofuran (concentration approximately 2X10- - 8X10-3M)

in a 50 ml round bottom flask filled with a reflux condenser, and

12

stOpcock. The st0pcock was closed with a serum cap. The solution

was stirred with a magnetic stirrer. To the solution was added

0.5-2ml of m 1.5 M alcoholic solution of sodium hydroxide. The
solution was warmed to m 600C and the diamine (approximately .3 M -

.6 M) was injected into the mixture with a syringe, and within seconds
the solution started to reflux. At this time (zero time for

reaction) 0.2 - 0.5 ml of sample (depending on the original concentration
of NiMMK) was removed with a microsyringe from the flask through the
serum cap of the side arm. The sample was diluted with tetrahydrofuran
to approximately 8 X 10—5 M in complex, and then transfered to a
spectraphotometer cell, with a l Cm. path length, placed into the
spectrophotometer, and the spectrum recorded (Unicam) or absorption

at 500, 400, 385, 360 and 340 nm. measured (Beckman). Total run times
ranged from 18 hours at high diamine concentration to m 24 hours at

low diamine concentration.

CHAPTER THREE

KINETICS AND DATA TREATMENT

I. The Kinetics of the Reactions of NiMMK

 

with 1,3 PrOpanediamine

 

The experimental procedure outlined for following the
reaction between NiMMK and 1,3—propanediamine in tetrahydrofuran
solution at 66°C results in a series of spectra (Figure I). Over
a period of time the decrease in absorbance at 385 nm is larger than
that at other wavelengths and the rate of reaction of NiMMK with
1,3-propanediamine may be followed at this point, (a typical data
set is shown in Table I), however, choosing any point between each
two isosbestic points is expected to show similar results, and they
do. The change of the spectra of the reactants as the reaction
progresses produces several sharp isosbestic points at 325, 418,

464 and 526 nm (see Figure I). These isosbestic points are coincident
to those obtained experimentally from the spectra of the NiMMK and pure
NiApSo (Figure II). This suggests a simple reaction between NiMMK

and 1,3-pr0panediamine. Reactions were run under pseudo first-order
conditions (31:200 NiMMK to 1,3-propanediamine) and therefore
1,3-pr0panediamine concentration can be considered to be constant. With
this assumption, the data are fitted to pseudo first-order rate
equation of the form (AaTAt/Aquo) = e-kt, where k is rate constant

and A“; At and A0 are the observed absorbances at infinite, t and

zero time (few seconds after mixing the reactants) respectively. By
using this equation rate constants were calculated by the curve

fitting program of Dye and Nicelygo. By feeding rate constant, time

and absorbance to the computer the computer adjusts them until the

13

14

calculated constant agrees with the experimental one. The calculated
and experimental data should nearly coincide if the form of the
equation being used in the curve fitting program is correct. A
sample plot of absorption vs. time, from the reaction between NiMMK

and 1,3-propanediamine is shown in Figure III.

15

FIGURE I

Absorption Spectrum for Reaction of NiMMK with 1,3-Propanediamine

16

I J L J 1

aoueqlosqe

 

 

0.2 -

350 400 450 ‘ 500 550 600
A (nm)

325

300

0.0

17

TABLE I
A Set of Kinetics Data for the Reaction
between NiMMK and 1,3-Pr0panediamine

Ann, 340 385 440 500

 

T% A

o\°
>

Time/Min A T% A T

 

0.0 1.075 8.75 1.280 5.35 0.668 21.75 0.521

 

 

14.66 1.015 8.90

H

.232 6.00 0.692 20.25 0.493

28.83 0.987 10.28

H

.175 6.90 0.713 19.50 0.469
42.16 0.958 11.10 1.120 7.90 0.734 18.75 0.451
53.83 0.942 11.50 1.080 3.50 0.752 17.90 0.435
68.50 0.938 11.90 1.050 9.10 0.778 17.00 0.419
85.16 0.910 12.38 1.008 9.98 0.790 16.25 0.399

110.16 0.878 13.50 0.962 11.00 0.802 15.90 0.375

140.16 0.842 14.45 0.910 12.40 0.828 15.00 0.355

175.16 0.812 15.60 0.865 13.80 0.842 14.70 0.336

213.83 0.800 16.00 0.838 14.80 0.862 13.92 0.324

255.50 0.812 15.35 0.817 15.30 0.878 13.40 0.315

325.50 0.779 16.80 0.797 16.10 0.886 13.10 0.302

508.83 0.768 17.10 0.772 17.00 0.897 12.90 0.291

1255.50 0.768 17.10 0.769 17.10 0.897 12.90 0.211

 

 

 

 

 

 

 

 

 

 

 

 

18

FIGURE II
Absorption Spectrum of Equal Concentrations

of NiMMK,(a) and NiApSo,(b)

19

000

own

con

onv

3.5 4
on:V

own

man

000

mum

 

 

0.0
N6
‘0
0.0
m6
0.—
a;
V.—
o;
w.—

 

0d

aoueqlosqe

20

FIGURE III
A Computer Plot of Absorbance vs. Time of the Reaction

between NiMMK and 1,3-Propanediamine

21

ohoIoF ho UdDFUanwh x34kwa #1 XII—Z u06m30¢mmco aeoneoaccooeeeeooeoe

o
x

 

11m

II
M“)

OX

X0

X0

tr- r . AU‘W—U‘MWLPMLPWMUWH
OK

xo

 

ll
“‘1‘ wu-wutwwu‘wuywuw?w

I—u-r—OI—O—wf fl...
OX

 

 

> (hgmo >m x (hAMO wtdm ka 2a m < hzmoa Duh44304<u oz< 4<h2uz~aumx 24
.OMhFOJQ mu Gamma 2w!) 0mm: m— n >Jzov hzmoa awh< DUJ<U < m2<wz o .hzuoa 4<h2utumwax 2<

a.
m.

m

22

A. 1,3-Pr0panediamine Dependence of the Rate
The reaction procedure has been outlined previously. Table 11
records the rate constants that are obtained with different concentra-

tions of 1,3-propanediamine.

TABLE II

1,3—Propanediamine Dependence of the Rate

 

 

[l,3-propanediamine]mole lit.1 kobs(min_1) standard deviation %
0.53 0.327 :5
0.663 0.510 :3
0.796 0.532 :6
0.884 0.713 +4

In Figure IV a plot of 1,3—propanediamine concentration vs. kObs is

shown. This suggests a first order reaction with respect to amine.

B. NiMMK Dependence of the Rate

 

The rate constants obtained in differenc concentrations of

NiMMK are shown in Table III.

23

FIGURE IV

A Plot of k0 5 vs. 1,3-Propanediamine Concentration

b

for the Reaction between NiMMK and 1,3-Pr0panediamine

24

w;

0.

p

3-... 26372553250: a:

V.—
_

N.—

o.—

4

ad

a

0.0

‘0

N6

v.0

0.0

m.o

o._

 

a;

2

bsX 10(minr')

4.

25

TABLE III

NiMMK Dependence of the Rate

 

 

 

[NiMMK] x 102(mole lit-1) kobs x 102(min71) standard deviation %
0.185 0.89 12.0
0.370 0.89 _+_3.0
0.740 0.89 +2.0

Since the calculation of k0 includes the concentration of NiMMK, the

b5

above data suggest an order of one with respect to the NiMMK concentration.

C. Sodium Hydroxide Dependence of the Rate

 

During the experiment it was found that the rate of the
reaction is dependent on the sodium hydroxide concentration. The

experimental results are shown in Table IV.
TABLE IV

Sodium Hydroxide Dependence of the Rate

[NaOH] x 102(mole lit—1) k x 102(min-1) standard deviation %

 

 

 

obs
0.30 0.820 14.0
0.41 0.934 :4.0
0.51 0.980 :2.0
0.62 0.989 +2.0

0.72 0.990 +4.0

26

A plot of observed rate constant vs. sodium hydroxide
concentration is shown in Figure V. The rate initially increases as
sodium hydroxide concentration increases, however, at higher concentra—
tions of sodium hydroxide the rate stays almost constant. More
experimental results have shown that this is due to an inhibitory
effect of the ethanol in which the sodium hydroxide is dissolved.

By increasing the sodium hydroxide concentration, consequently the
concentration of ethanol increases and therefore the rate decreases.
A third order rate constant calculated from the 510pe of the hydroxide

dependence is 1.72 litzmolemzmin.1

27

FIGURE V

A Plot of kb vs. Sodium Hydroxide Concentration
o s

for the Reaction between NiMMK and 1,3-Pr0panediamine

28

o.—

0.0

M

m6
A

nd

a

C: 6.95.2 x Toni

0.0

1

m6

1

Yo

_

I «.0

1 V6

1 0.0

l ”.0

 

éobsX102(min")

29

2. Kinetics of the Reaction of NiMMK with Ethylenediamine

The reaction of NiMMK with ethylenediamine in tetrahydro—
furan produces a series of spectra (a typical sample is shown in
Figure VI). There are three important pieces of information that may
be obtained from this series:

i. The absorbance at 360 nm initially decreases and is
then followed by the appearance of an isosbestic point (see Figure VI
and Table V at 360 nm).

ii. The absorbance at 340 nm initially decreases (spectra
1,2,3 and 4 of Figure VI) and then increases as the reaction proceeds.

iii. Reaction of NiMMK with ethylenediamine does not produce
the predicted isobestic points at 299, 360, 422, 476 and 519 nm based
on spectra of NiMMK and NiMcyclo-l3 (see Figure VII).

These phenomena were not observed in the reaction of NiMMK
with 1,3-pr0panediamine and are thus evidence for greater complexity
of this reaction compared with the simple reaction with 1,3-propanediamine.
Similar to the spectrum number five of figure V1 is spectrum number six
from Figure I, which is the final product in reaction of NiMMK
with 1,3-pr0panediamine. The spectra suggest that the reaction of
NiMMK with ethylenediamine occurs via a two step process in which
a significant concentration of the "intermediate" builds up as the
reaction proceeds.

Reactions were run under pseudo first-order conditions
(by making ethylenediamine concentrations approximately 200 fold
larger than NiMMK concentrations). A typical set of data is in
Table V. The two steps were treated separately and each step was

fitted to a pseudo first-order rate equation by the procedure

30

previously mentioned. Figures VIII and IX show the computer plot

of absorbance vs. time for the first and second steps respectively.

31

TABLE V
A Set of Kinetics Data of the Reaction

of NiMMK with Ethylenediamine

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Ann. 340 360 385 440 500
Time/Min A T8 A T8 A T8 A T8 A T8
0.0 1.048 9.10 0.962 11.00 1.200 5.15 0.648 22.90 0.505 31.30
16.0 0.999 10.10 0.917 12.10 1.140 7.45 0.671 21.20 0.468 34.10
27.66 1.000 10.0 0.885 13.00 1.018 8.90 0.694 20.25 0.448 36.00
39.33 1.015 9.90 0.8810 13.11 1.000 10.00 0.723 19.00 0.435 37.00
52.33 1.038 9.50 0.860 14.00 ‘0.936 11.90 0.735 18.60 0.418 38.60
66.0 1.050 9.00 0.868 13.80 0.878 13.25 0.762 17.45 .411 39.00
78.66 1.072 8.70 0.860 14.00 0.819 15.10 0.769 17.10 .397 40.10
91.66 1.110 7.92 0.863 13.90 0.790 16.30 0.795 16.10 .392 40.16
108.33 1.150 7.10 0.866 13.60 0.739 18.45 0.810 15.70 .391 40.90
125.16 1.190 7.50 0.850 14.10 0.671 21.40 0.796 16.10 .384 42.70
141.83 1.220 6.10 0.865 13.90 0.661 21.90 0.837 14.90 0,379 141.50
161.83 1.240 5.92 0.866 13.85 0.619 24.10 0.842 14.30 .371 41.90
183.5 1.245 5.90 0.866 13.85 0.588 25.92 0.878 14.10 .372 42.80
208.5 1.290 5.10 0.866 13.85 F0.561 27.65 0.859 14.00 .373 42.60
258.5 1.310 5.00 0.890 13.00 0.530 29.80 0.879 13.25 .366 42.60
316.83 1.340 4.90 0.890 13.00 0.510 31.75 0.862 13.90 .371 43.00
386.83 1.350 4.75 0.890 13.00 0.491 32.10 0.882 13.10 .369 42.50
685.16 1.351 4.60 0.900 12.80 0.477 33.72 0.883 13.00 .371 42.90
1298.5 1.370 4.40 0.900 12.80 0.473 33.90 0.898 12.90 .366 42.50
1570.16 - - .900 12.80 0.471 34.00 — - - -

 

 

32

FIGURE VI

Absorption Spectrum of the Reaction of NiMMK with Ethylenediamine

33

onm.

AEcV<

 

000

con

03.

00V

own

man

com

 

mNN

 

0.0
«.0
v.0

m6
o._
m.—
v.9
0;
m;

ON

89

O

SOUBQJ

34

FIGURE VII
Absorption Spectrum of Equal Concentrations

of NiMMK(a) and MiMcyclo-13(b)

35

000

own

00m.

onv

The: 4

oov

own

man

oon

 

nun

0.0
Nd
v.0
0.0
m6

0;

NA

 

 

aoueqlosqe

36

FIGURE VIII
A Computer Plot of Absorbance vs. Time
for the First Step of the Reaction

of NiMMK and Ethylenediamine

37

wabhuanrup xzaumu hd on. 1.». wZ—I¢~CZUJ>IhU kc onNo- 924 XII~2 kc. ¢OCN~N06 ooeoeuocooooooeooooooooe OPm

0..--U00-0“-I-0m--00m0l'00“----m----m---DVD'--V'--0V0'--m----m--l-m--'-V'-nu0U---’Wl--'v-lu--w-Incl-m0---—

CKU‘

 

 

)(C

‘ \u—O—u-OHLha-u—o— t—u

x:

x
:
C:

0--- t—C—t-U' o—o—u—o—o‘rv—u—u—u—U hot- v-vo—u‘u—a- u—u—U‘ o—o—u— o—U‘u—n—n—bU‘ u—e—u—n—U‘ u—u—u—u-mwu-u—wlr—

 

> (bdmc 2; x (bauc utdm MI» 2— we: hz—Cn cuhdJDUTEU c2< J<b2wx~awaxw (c V2<ux u
Acmphcgn Vb c—mwa 2.543 Cum: m~ u >42»: bzucn Hakka-.9130 d v2¢u1 o ohz—Oa Adpzwi~mu0xu ‘4 $233. x

38

FIGURE IX
A Computer Plot of Absorbance vs. Time
for the Second Step of the Reaction

of NiMMK and Ethylenediamine

39

umDhmoaym» xDqkwo h< ouoIoho m2»34—szd%rww uC oJroxo C24 :27“? uCorcccdwc. finuuueocusooaau003n:oaoo

b

-1:-u-11-muu-1m-1--w-1u1¢--11m111-muu-u0-111m111101111m-uuumuus1muuuuw11-10---

N 111

Cr.

C
K

t—v—b-o—b-U‘ r—b— h-h-‘U‘D—D—hur-U‘O—a—v—u—U‘ I—ID—w—h—Lr‘D—D-D—D-‘Lf I—h-v—h-LrD—r—D—Hl! v—u—u—u—(r u—r—u-nb-u‘u—
D-CI-oh—HD-IU‘HoupceaU‘t—nt—‘HHU'puHhh.U‘pa~~~JVHh4D-~U‘ O-‘Dc-b—a-o-u .HD—vl- h-n‘llb-CO—nhh—u‘t-‘vuh 0. «U

m-»--m-11-0---1m----m---10----m1111mu-u-m1-uum11u-0----m--u-mu---r1-uum--o-011-10----m1111m1111m---

> <p4uc >u x dwguc mfdm wI» Zn wad kzpco Ow

. . - - kq43644u c2: J<brm3~1w
.cmbpcoo v_ c~vua 2dr: Cum: 0" u >42c. hzwca ompquzu_<u q vzquz o .»

xu Ac

I...“
zhca uqkzuabaueum ru

40

A. Ethylenediamine Dependence of the Reaction Rate

 

The experimental data for ethylenediamine dependence of the
first and second steps are tabulated in Table VI. The second order
Arate constants are obtained by plotting observed rate constants vs.
ethylenediamine concentrations (Figures X and XI). Their values are

-1 . - - - - _
0.19X10 liters mole 1 min 1 and 0.16x10 1 liters mole 1 min 1

respectively.

B. NiMMK Dependence of the Reaction Rate

 

By holding ethylenediamine and sodium hydroxide concentrations
constant the following results have been obtained by varying the NiMMK

concentration (the results are shown in Table VI).

41

TABLE VI
[Ethylenediamine] Dependence of the First and Second Steps

a. First Stage

 

 

 

[en] mole lit-1 kobs x 10 (min ) standard deviation %
0.38 0.90 $7.0
0.47 1.16 17.0
0.57 1.44 $4.0
0.66 1.68 16.0

b. Second Stage

0.38 0.70 .5.0
0.47 0.79 33.0
0.57 1.07 19.0

0.66 1.14 $10.0

42

TABLE VII

[NiMMK] Dependence of the First and Second Step
a. First Stage

 

 

 

[NiMMK] x 102M kobs x 101(min-1) standard deviation 8
0.159 0.142 13.0
0.318 0.144 t4.0
0.477 0.141 16.0
0.636 0.143 t5.0

b. Second Stage

0.159 0.108 13.0
0.318 0.107 $8.0
0.477 0.107 14.0

0 636 0 107 $4.0

43

FIGURE X

Ethylenediamine Dependence of the Rate of the First Step

44

A_.:._ 0.02 V _Hcou

 

o.— a. m. h. o. m: m. N. p.
. u m a . J 4 _ q \M
\\
L V.
\\
. m
75870.9: 30:. Top x0_ 00*
owe: 3...: of *o oucopcoaov co \
\ I. m.

' 1 P. _SQO
('_u.w)z0lx _ y

1
‘0.
.—

 

ON

Ya

 

45

FIGURE XI

Ethylenediamine Dependence of the Rate of the Second Step

46

C: 6.63 mi

 

O; 0. m. h. 0. w. V. m. N. _..
1 _ _ . _ _ _ a a A
\
\
\
\
\
\
\
\
\
\
a \\
.EE mo 20. . u
7. 7.2. £73332. .94 \
emu: 953... of *o oucopcoaop co \\
\
\
\
\
\
\
\
\

 

a;

V4

47

C. Sodium Hydroxide Dependence of the Reaction Rate

 

The rates of both the first and the second steps are dependent
on the sodium hydroxide concentration, similar to that found for the
reaction between NiMMK and 1,3-propanediamine; the rate stays
constant at higher hydroxide concentration. The resulting rate
constants are tabulated in Table VIII a and b. Figure XII shows the
plot of ln(A0° - At/A0° - A0) vs. time. The slope of these lines are
pseudo first-order rate constants at different concentrations of
sodium hydroxide. A plot of the observed rate constant vs. sodium
hydroxide concentration for both steps are shown in Figures XII and
XIV.

As was mentioned earlier, by increasing the sodium hydroxide
concentration, the concentration of the ethanol in the reaction
mixture increases, and due to its inhibitory property, rate decreases
(as is shown in Figures XIII and XIV). The estimated third order

rate constants for the first and the second stage are 32.93 lit2

mole.2 min-1 and 11.65 lit2 mole-2 min1 respectively.

48

TABLE VIII
[Sodium Hydroxide] Dependence of the First and Second Step

a. First Stage

 

 

 

2 k x 102min-1 - -
[0H]_x 10 M obs standard deV1at1on %
0.092 2.95 :3.0
0.123 3.60 :4.0
0.185 3.70 :4.0
0.246 3.70 :5.0
0.308 3.80 +4.0

b. Second Stage

0.092 0.43 :6.0
0.123 0.66 :3.0
0.185 1.05 :3.0
0.308 1.26 +3.0

0.401 1.29 +2.0

49

FIGURE XII

Sodium Hydroxide Dependence of the Rate for the Second Step

50

72x 25 m2:

 

 

 

_ _ q _ n _ _ q _ _ _ _ _
r. L
/
I / II
1 / A
/
l I l
/
/
I / 1
m; c
/
1 0.. . X ..
/
o. I u /
/.
I V. o “I .. I.
o
m. I
./
p F L _ _ _ _ r _ _ _ _ . .I/
on on mm. mV vv ov on an an Va on 0.. up w

oi

9n

«6

mfi

Ya

o.u n

v U
‘v-“v "

o.—

m.—

 

51

FIGURE XIII
Sodium Hydroxide Dependence of the First Step

for the Reaction between NiMMK and Ethylenediamine

52

m0

FE 6.95 . o. x Toni

m0 «.0 _.0

_ _ —

 

:8 8R

 

—.0

«.0

m0

V.0

n0

0.0

«.0

éobs x10'(min")

53

FIGURE XIV
Sodium Hydroxide Dependence of the Second Step

for the Reaction between NiMMK and Ethylenediamine

54

0.0

V0

ATE «_oEvaop x 7.002;

«.0 «.0

—.0

 

«.0

V0

'°.
0

“3
o

O

«.—

 

(min?)

-2

tabs X10

CHAPTER FOUR

MECHANISM OF THE REACTIONS

The reaction of NiMMK with amines results in the formation
of two types of complexes, the macrocyle (X) and non-cyclic (XI)
complexes. These compounds are obtained by the condensation of
the CO group(s) of NiMMK with one or two amine groups and the
elimination of one or two molecules of water35’36.

With 1,3-propanediamine, only one of the CO groups has
undergone condensation, whereas with ethylenediamine both of the C0
groups have taken part in the condensation reaction (compare Figures I
and VI). It thus appears that the ring closure reaction proceeds

via a stepwise process in which the coordinated C0 groups react

succesively.

55

56

 

 

Ph Ph
K" 7"“ \ /
c=C C=C
/ \ / \N
N N \
Ni ' Me H N-x-NH . N1 /Me
/ \ C a x / / \
o N/ \Me / o N Me
I '1 “2“ I u
c N c N
/ \C/ x11 P/ \C/ XIII
Ph 11
/ Ph
Ph
Ph Ph
\ /
C=C\
/ w
N
N\ \N

/ \C/ XIV

57

Since the CO groups are of different types, one is part of
a five membered chelate ring; 'the other part of a six-membered ring
their reactivities may be different. By study of the fragmentation
pattern of the mass spectrum of NiApSo it seems that the fragments of
the six-membered ring predominates (see Table IX), and thus we
conclude that the CO groups of the five membered ring preferentially
reacts faster. The data obtained from the fragmentation pattern
of this compound are shown in Table IX.

Although attempts to isolate the intermediate species in
the ring closure reaction have not been successful, there are

indications for the existance of intermediate in the reaction mixture.

Benzoyl Derivative of the Intermediate

 

100 m. of 1 3.3 x 10.3 M solution of NiMMK in acetonitrile
and ethylenediamine (0.6M) were mixed, and refluxed. The reaction
was followed by Unicam spectr0photometer until the spectrum of the
reaction mixture was close to the spectrum of the NiApSo (see
spectrum number 5 of Figure VI). At this time the reaction mixture was
cooled to prevent the progress of the reaction. 1.5 ml of benzoyl
chloride was added to a solution of 15 ml chloroform and 60 ml of a
5% solution of sodium hydroxide. This mixture was then added to the
quenched solution of the reaction mixture. The solution was stirred
for about twenty minutes at room temperature and then allowed to
stand for twelve hours in a separatory funnel. The higher level of
Sparatory funnel was evaporated and then introduced to the mass
spectrometer. The Spectra showed a benzoyl derivative of the

dangling complex (XV, M.W = 690).

58

XV

ul/cx
.. N4 /
P/ \ NHN
c /
= /i\ C/h
C \N \\ P
%\ /N /.OIIIC/
f Rn
NIH

59

TABLE IX

Mass Spectrum of NiApSo

 

 

 

m/ea Assignment Leaving Group Assignment Residue
p-lS -CH3
p~28 N2
p-84 N=N-CII(CH3)2
N
p-159 Ph-C-NzN-C(CH3)2
p-l87 Ph-C-N=N-C(CH3)2-N=N
b
p-250 Ph-C-C(Ph)-N-(CH2)3-NH2
p—276 Ph-C=C(Ph)N=N-C(CH3)2
p-290 Ph-C(N)=C(Ph)N=N-C(CH3)2
’ ===N Me
. \ / ]
O/N1\N/C\Me
350 I
c '1
/ \C/
Ph /
L Ph
I /N'-N
N‘\
308 0/ N
I II
/C kc/ N
Ph I
L Ph

 

 

 

 

’

60

TABLE IX

Continued

 

 

 

 

 

 

 

 

 

 

m/e Assignment Leaving Group Assignment Residue
f r’N ] +
/ Ni\
9 1.
294 C N
/ \\ C/
Ph I
Ph
k I
+
- I
[ /N1\
1 ’1
280 C N
/'§§C./’
Ph 1
Ph
p I
236 [Ni-N-C(Ph)-C(Ph)]+
222 [O-C(Ph) = C(Ph)-N = N]+
+
F .
N1 ]
H—w/ \N
202 g "
N
./ §§13/’
Ph 1
7 Ph I
178 [PhC(NH)CPh]+
77 1PM“
a. for nickel containing species the value for 58N is given
b. for dangling compounds only

61

The experimental results (based on the dependence of the
rate of the reaction on the concentration of amines, NiMMK and sodium
hydroxide) have shown that for each stage the overall reaction is a
third order, and is first order with respect to each of the reactants.

A mechanism consistent with the observed results and a
derivation of the rate equation is suggested as follows:

a. For 1,3-pr0panediamine and NiMMK reactions:
k

 

 

f
NiMMK + am :———l—> NiMMK. am fast (1)
k
f2
kb
NiMMK. am +()H- < 1 > [NiMMK(am-H)]-+ H20 fast (2)
k
b2
-k -
[NiMMK(am-H)] > Nidang + 0H slow (3)
¢i§l93951-= k [NiMMK(am-H)]'
dt 1

from 2

= [NiMMK(am-H)]'[H20]

 

Kb

[nnmx.am][mfi

[NiMMK(am-H)]-= Kb[%E%]' . [NiMMK . am]
2

d o — a
My?“ ) = 85113—20? W“ 3“”

from I

assume

Therefore

But

Therefore

62

[NiMMK. am] = Kf[NiMMK][am]

diߤ%3281.= lebe [3301" [NiMMK](am]

k3 = lebe

W = k3 [on] [NiMMK][am]/H20

For ethylenediamine and NiMMK reaction:

 

 

 

 

 

K
[Nidang] + OH' > H20 + [Nidang]- fast (4)
- k —
[Nidang ] > NiMcycle + OH slow (5)
d(NiMcycle) _ . -
dt - k2[N1dang ]
[H20][Nidang-]
K =
[0H][Nidang]
[Nidang-] = K[0H1[Nidang]
H20

d(NiMeycle) = k K [OH][Nidang]

dt
H20

 

CHAPTER FIVE
SUGGESTIONS FOR FUTURE WORK

In addition to the determination of the activation energy,
entrOpy and ethalpy of the reaction of diamines with NiMMK, there are
several other areas that should be investigated.

Fragmentation pattern of NiApSo in mass spectrometer
shows that the site of the first condensation is the five-membered
chelate ring, rather than the six-membered ring (see Table IX).

Work has to be done on the crystal structure of NiApSo to support the
idea; we are in the process of doing this.

We have also examined successfully reactions of 1,2-
pr0panediamine with NiMMK and ethylenediamine with NiDMK (VII where
R3 and R4 are methyl groups) in tetrahydrofuran. Their absorption
spectra are shown in Figures XV and XVI respectively. Understanding
their mechanism of the reaction needs more kinetics data; however
reactions of NiMMK with 1,2 propanediamine shows very similar

paths to those of NiMMK with ethylenediamine (compare Figures VI

and XV).

63

64

FIGURE XV

Absorption Spectrum for Reaction of NiMMK with 1,2-PrOpanediamine

2.0

1.6 -

6S

eoueqlosqe

 

_

 

250 275 300 325 350 400 450
A(nm)

225

200

66

FIGURE XVI

Absorption Spectrum for Reactions of NiDMK with Ethylenediamine

67

 

aoueqlosqe

 

300 325 350 400 450 500 550 600
A (nm)

275

APPENDIX

APPENDIX

During the preparation of this thesis we became aware of the

*
Tektronix 4012 graphics terminal. Reexamination of the kinetics data

was carried out. The resulting plots obtained from the plotter are

shown in Figures XVII-XXT* The program used for the plots is also

included.

Figure

Figure

I:igure

f2igure

XVII

XVIII

XIX

XX

[NiMMK] Dependence for the Reaction between
1,3-Pr0panediamine and NiMMK

[Sodium Hydroxide] Dependence for the First

Step of the Reaction between NiMMK and Ethylenediamine
[NiMMK] Dependence for the Second Stage of the
Reaction between NiMMK and Ethylenediamine

[Sodium Hydroxide] Dependence for the Reaction

between NiMMK and 1,3-Pr0panediamine

*553]pecial thanks to Lawrence Pachla for this information.

*R-

‘jrhe dotted line indicates the theoretical values; the triangles
indicate the experimental values.

68

XM I N -
XMHX -
\"I‘l I N -
VHF-1X '-

HBSORBRHCE

p

p

 

600903 1.111 )-
.ser+oo U12)-
.1seE+01

69

FIGURE XVII

ABS vs T
CONTl- .1880E+01
.7634E+00
.89008-08
. p..
.n
....
.,.‘_.

1 A A A A A A

TIME (MIN)

 

70

 

FIGURE XVIII
ABS vs T
XHIH- 0. CONTl- .7870E+00
XMRX- .100E+03 U(1)- .10866+01
YNIN- .70®E+00 U(8)- .3834E-01
vmex- .1IOE+01
‘1
P .‘.
0A
> ".
m: QOF‘BAHCE .
flI
#- ‘. .
b ...‘
a“
b .°'-..
.0...
+ g... 0
TIME (MIN)

71

 

FIGURE XIX
ABS 05 T
XMIN- e CONTI- .6630E+00
xmex- 3805+03 0(11- .4aeeE+oe
mm- .400E+00 U(c?.)- . 1082E-01
vmnx- .7er+ee
b:
5
3.
'11
HBSORBANCE . '.
'x
r ‘.
L
r "3:-.,
.. C...‘ . .. .
. "" ------ o...

 

TIME (MIN)

72

FIGURE xx
ass 03 T
xmrn- e. CONTI- .13aeE+eI
xmax- .7seE+03 lJ(1)- .833SE+00
YMIN- 7006+00 U(2)- .9844E-oa
vmax- .140E+01
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s
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0‘.
L ..
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. . . . A ' . 0..

 

 

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BIBLIOGRAPHY

E;

 

(1)
(2)

(3)
(4)
(5)

(6)

(7)
(8)
(9)
(10)

(11)

(12)

(13)

C14)
(15)
C16)
(17)
(.18)

(19)

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(20)

(21)

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