• TABLE OF CONTENTS
HIDE
 Title Page
 Acknowledgement
 Table of Contents
 List of Tables
 List of Figures
 Introduction
 Experimental procedures
 Results
 Discussion
 Summary
 Bibliography
 Appendices
 Biographical sketch














Title: Complexes of iron (II) cobalt (II) nickel (II) and copper (II) with 2-(α-pyridylmethyleneaminomethyl)-pyridine
CITATION PDF VIEWER THUMBNAILS PAGE IMAGE ZOOMABLE
Full Citation
STANDARD VIEW MARC VIEW
Permanent Link: http://ufdc.ufl.edu/UF00097940/00001
 Material Information
Title: Complexes of iron (II) cobalt (II) nickel (II) and copper (II) with 2-(α-pyridylmethyleneaminomethyl)-pyridine
Physical Description: vi, 53 l. : illus. ; 28 cm.
Language: English
Creator: Petrofsky, James Leroy, 1938-
Publisher: s.n.
Place of Publication: Gainesville
Publication Date: 1964
Copyright Date: 1964
 Subjects
Subject: Coordination compounds   ( lcsh )
Transition metal compounds   ( lcsh )
Chemistry thesis Ph. D
Dissertations, Academic -- Chemistry -- UF
Genre: bibliography   ( marcgt )
non-fiction   ( marcgt )
 Notes
Thesis: Thesis - University of Florida.
Bibliography: Bibliography: l. 41-43.
Additional Physical Form: Also available on World Wide Web
General Note: Manuscript copy.
General Note: Vita.
 Record Information
Bibliographic ID: UF00097940
Volume ID: VID00001
Source Institution: University of Florida
Holding Location: University of Florida
Rights Management: All rights reserved by the source institution and holding location.
Resource Identifier: alephbibnum - 000423999
oclc - 11062827
notis - ACH2404

Downloads

This item has the following downloads:

PDF ( 1 MBs ) ( PDF )


Table of Contents
    Title Page
        Page i
        Page i-a
    Acknowledgement
        Page ii
    Table of Contents
        Page iii
    List of Tables
        Page iv
        Page v
    List of Figures
        Page vi
    Introduction
        Page 1
        Page 2
        Page 3
        Page 4
        Page 5
    Experimental procedures
        Page 6
        Page 7
        Page 8
        Page 9
        Page 10
    Results
        Page 11
        Page 12
        Page 13
        Page 14
        Page 15
        Page 16
        Page 17
        Page 18
        Page 19
        Page 20
        Page 21
        Page 22
        Page 23
        Page 24
        Page 25
        Page 26
        Page 27
    Discussion
        Page 28
        Page 29
        Page 30
        Page 31
        Page 32
        Page 33
        Page 34
        Page 35
        Page 36
        Page 37
        Page 38
    Summary
        Page 39
        Page 40
    Bibliography
        Page 41
        Page 42
        Page 43
    Appendices
        Page 44
        Page 45
        Page 46
        Page 47
        Page 48
        Page 49
        Page 50
        Page 51
        Page 52
    Biographical sketch
        Page 53
        Page 54
        Page 55
Full Text










COMPLEXES OF IRON(II) COBALT(II)
NICKEL(II) AND COPPER(II) WITH
2- (oc-PYRIDYLMETHYLENEAMINOMETHYL)-
PYRIDINE













By
JAMES LEROY PETROFSKY










A DISSERTATION PRESENTED TO THE GRADUATE COUNCIL OF
THE UNIVERSITY OF FLORIDA
IN PARTIAL FULFILLMENT OF THE REQUIREMENTS FOR THE
DECREE OF DOCTOR OF PHILOSOPHY










UNIVERSITY OF FLORIDA
December, 1964


















































UNIVERSITY OF FLORIDA

11 1" l I2 I I I2638 I
3 1262 08552 2638












ACKNOWLEDGMENTS


The author acknowledges the help of all those

persons who have made this work possible, and especially

wishes to extend his appreciation to Mrs. Edwin N.

Johnston who typed this manuscript.













TABLE OF CONTENTS


Page

ACKNOWLEDGMENTS . . . . ii

LIST OF TABLES. . . . . .. iv

LIST OF FIGURES . . . ... vi

INTRODUCTION. . . . . 1

EXPERIMENTAL PROCEDURES . . . 6

RESULTS . . . . ... . 11

DISCUSSION. . . . . ... 28

SUMMARY . . . . . 39

BIBLIOGRAPHY. . . . . 41

APPENDICES . . . . ... ... 44

BIOGRAPHICAL SKETCH . . . 51












LIST OF TABLES


Table Page

1. Magnetic Moments at 2990K . . .. 11

2. Curie and Weiss Constants for Normal
Temperature Dependent Complexes ...... 12

3. Variation of Molar Susceptibilities and
Magnetic Moments of [Fe(PMP)C12] with
Temperature . . . . 17

4. Variation of Molar Susceptibilities and
Magnetic Moments of [Co(PMP)2]C12 with
Temperature . . . ... 18

5. Variation of Molar Susceptibilities and
Magnetic Moments of [Ni(PMP)2]C12 with
Temperature . . . .. 19

6. Variation of Molar Susceptibilities and
Magnetic Moments of [Cu(PvP)C1]Cl with
Temperature . . . .. 20

7. Specific Conductances at 250C ....... 21

8. Molecular Weights . . ... 22

9. Absorption Maxima and Molar Extinction
Coefficients Determined from the Ultra-Violet
Spectra of Ligand and Complexes . 23

10. Absorption Kaxi:a and Molar Extinction
Coefficients Determined from the Visible
Spectra of Lig&nd and Complexes . 24

11. Absorption Maxima Determined from the Solid
State Visible Spectra of the Complexes. 25

12. Absorption Max:ima Determined front the Lolid
State Near Infrared Spectra of the Complexes. 26

13. Infrared Absorption Bands (cm.-1) for 2-(a-
Pyridylmethyleneaminomethyl)-Pyridine and
Its Complexes . . . ... 27










Table Page

14. Field Strength as a Function of Current as
Determined with Water . . .. 46

15. Field Strength as a Function of Current as
Determined with Nickel Ammonium Sulfate-6-
Hydrate . . . .... ... 47

16. Average Field Strength as a Function of Current 48

17. Temperature Dependent Diamagnetic Corrections
for a Quartz Gouy Tube. . . ... 49

18. Pascal's Corrections for Diamagnetism ... .50

19. Specific Conductances at 25C . ... .51

20. Molecular Weights . . . ... .52












LIST OF FIGURES


Figure Page

1. Temperature Dependent Susceptibility of
[Fe(PMP)C12] . . . . 15
2. Temperature Dependent Susceptibility of
[Co(PMP)2]C12. . . . .. 14
5. Temperature Dependent Susceptibility of
[Ni(PMP)2JC12 . . . ... 15
4. Temperature Dependent Susceptibility of
[Cu(PMP)Cl]C1. . . . ... 16

5. Energy States Which Arise From the F and P
Term States of a d Ion in a Regular and
Tetragonally Distorted Octahedral Field. 32

6. Partial Energy Level Diagram for a d8 Ion in
an Octahedral Field, Showing the Triplet
States and the Lowest Singlet State. ... 34

7. Energy States Which Arise From the 3H and 5D
Term States of a d6 Ion in a Regular and
Trigonally Distorted Octahedral Weak Field .. 36
8. Energy States Which Arise From the 2D Term
State of a d9 Ion in a Regular and
Tetragonally Distorted Octahedral Field. .. 37












INTRODUCTION


In the past 60 years there has been a great increase

in interest in coordination compounds, particularly those

of the transition metals. This increasing interest can be

credited to the work of Alfred Werner, who did much in the

way of developing and correlating valency and stereo-

chemistry (40,41). In more recent years a number of

investigations have been concerned with the magnetic prop-

erties of inorganic complexes, since the effective magnetic

moment of an atom can be correlated with the bond type,

coordination number, and stereochemistry of the atom (3,5,

6,7,8,15,35).
The purpose of the present investigation is to

prepare complexes of iron(II), cobalt(II), nickel(II) and

copper(II) chloride with the tridentate ligand 2-(a-

pyridylmethyleneaminomethyl)pyridine (Structure I), which

contains the -N=C-C=N-C-C=N- group, and to investigate

their stereochemistry by means of magnetic, spectral and

conductivity measurements. (The iron(II) perchlorate

complex has been prepared (27) but the only study made of

it was a determination of the room temperature magnetic

moment.) This ligand contains three donor nitrogen atoms








2

and is constitutionally similar to that ligand which is

familiarly known as terpyridine (2,6-bis-(a-pyridyl)-

pyridine) (Structure II).

Terpyridine is a most important tridentate chelate

compound that has been extensively studied. In 1953 a

brief report was made on the preparation and use of 8-

(a-pyridylmethyleneamino)quinoline (Structure III) as a

tridentate chelate compound (11). This compound is consti-

tutionally similar to terpyridine and so coordinates to

iron(II) salts to give analogous diamagnetic complexes.

All of these tridentates are slightly acidic in

that bases can remove one proton per coordinated tridentate

residue from the complexes. Removal of the proton enhances

conjugation and thus a greater resemblance to terpyridine

complexes. An excellent example of this is the condensa-

tion product of 2-pyridinaldehyde with 2-pyridylhydrazine

to form 1,3-bis-(2'-pyridyl)-2,3-diaza-l-propene (16)

(Structure IV).

In any consideration of design of new tridentate

chelate compounds related to terpyridine, cognizance must

be taken of the availability of pyridine-2,6-dialdehyde

(Structure V), which will condense with primary amines to

give Schiff bases of the general formula VI, in which

there is the same sequence of donor atoms and bonds as in

terpyridine. When R=methyl, ethyl, phenyl or benzyl











groups, this ligand coordinates readily to give typical

diamagnetic octahedral iron(II) complex salts, analogous

to those of terpyridine.

Among the condensation products obtainable from V

and primary amines are the linear polymers derivable from

diamines, e.g. hexamethylenediamine (Structure VII).

Reaction of this polymer with an excess of iron(II) sulfate

leads to a solid composed of one molecule of iron(II)

sulfate for each two residue of VII. This compound is

ferromagnetic with a molar susceptibility of 155,000 x 10-6

c.g.s. units, but no conclusions regarding the molecular

structure are drawn.

To understand the magnetic and spectral properties

of these coordination compounds, recourse must be had to

ligand field and molecular orbital theories (2,6,7,9,11,

14,18,23,25,28,29,30,31,32,36,38,39), the details of which

will not be given here. The magnetic susceptibilities

will be determined over a range of temperature since it is

difficult to properly evaluate magnetic data obtained at

room temperature only. It is now recognized that intra-

or intermolecular antiferromagnetic interactions exist in

a number of complexes and the existence of this phenomenon

can be proved only by magnetic measurements over a range

of temperature. A gross misinterpretation of the room

temperature magnetic moment can be made by assuming that











the ground state level of a transition metal ion is always

separated from the next higher level by h) > kT. However,

if the spectral measurements provide the necessary data

for an evaluation of the crystal field splitting, 10 D ,

then they will also reveal the energy of separation between

the ground state and the first excited state, thus allowing

a more accurate evaluation of the magnetic data. Spectral

measurements will be made both in solution and in the solid

state to determine any change in stereochemistry upon dis-

solution of the complexes. Conductivity measurements will

be made so as to determine whether or not the chloride

ions are outside of the primary coordination sphere. Thus

any change in stereochemistry upon dissolution, as revealed

by the spectral measurements, will be quite important here.










H


I
N H
I O1 H o N, l c
H


OHCO CHO


H
CH N..- N


HC- N CH
I I 11
RN_ N_R


H vN HC r CH
ii (I
S N_(CH2)6 _N N-


01-11 /-












EXPERIMENTAL PROCEDURES


Preparations and Analytical Data

Dichloro-2-(a-pyridylmethyleneaminomethyl)pyridine-

iron(II).--To two ml. of aminomethylpyridine (0.018 mole)

in 10 ml. of absolute ethanol was added 2 ml. of 2-

pyridinaldehyde (0.018 mole), and the solution was gently

refluxed 20 minutes and then cooled. To this was added

2.02 g. of iron(II) chloride tetrahydrate (0.009 mole)

dissolved in 20 ml. of absolute ethanol. Precipitation

was immediate and the slightly hygroscopic green-black

microcrystalline product was separated from the mixture by

filtering with suction, washed three times with 10 ml.

portions of absolute ethanol, and dried over P4010 in vacuo

for 12 hours at 25C. and for 12 hours at 800C. Anal.

Calcd. for [FeC12HllN3C12]'H20: C, 41.19; H, 3.22; N,

12.28. Found: C, 41.37; H, 3.81; N, 12.45.

Bis-[2-(a-pyridylmethyleneaminomethyl)pyridine-

cobalt(II) chloride.--To two ml. of aminomethylpyridine

(0.018 mole) in 10 ml. of absolute ethanol was added 2 ml.

of 2-pyridinaldehyde (0.018 mole) and the solution was

gently refluxed 20 minutes and then cooled. To this was

added 1.68 g. of cobalt(II) chloride hexahydrate (0.007










mole) dissolved in 20 ml. of absolute ethanol. After

cooling for 30 minutes precipitation was virtually complete

and the pink microcrystalline product was filtered off by

suction, recrystallized from absolute ethanol, washed with

three 10 ml. portions of absolute ethanol, and dried over

P4010 in vacuo for 12 hours at 250C. and for 12 hours at
8000. Anal. Calcd. for ECoC24H22N6IC12H20: C, 53.14;

H, 4.38; N, 14.88. Found: C, 53.35; H, 4.90; N, 14.69.

Bis-[2-(a-pyridylmethyleneaminomethyl)pyridine-

nickel(II) chloride.--This complex was prepared in a manner

analogous to that of the above cobalt(II) complex. Anal.

Calcd. for [NiC24H22N6]C12'H20: C, 53.24; H, 4.46; N,

15.00. Found: C, 52.91; H, 4.57; N, 14.79.

Chloro-2-(a-pyridylmethyleneaminomethyl)pyridine-

copper(II) chloride.--To two ml. of aminomethylpyridine

(0.018 mole) in 10 ml. of absolute ethanol was added 2 ml.

of 2-pyridinaldehyde (0.018 mole), and the solution was

gently refluxed 20 minutes and then cooled. To this was

added 1.36 g. of copper(II) chloride dihydrate (0.008

mole) without excessive stirring. After immediate precipi-

tation the excess liquid was decanted off, absolute ethanol

added, the mixture briskly stirred and cooled, and the pale

green microcrystalline product was then filtered off,

washed with three 10 ml. portions of absolute ethanol, and










dried over P4010 in vacuo for 12 hours at 250C. and for 12

hours at 800C. Anal. Calcd. for CCuC12H11N3C1]C1-H20:

C, 41.22; H, 3.72; N, 12.00. Found: C, 41.06; H, 3.31;

N, 11.80.

All analytical measurements were made by Galbraith

Microanalytical Laboratories, Knoxville, Tennessee.


Annaratus

Magnet.--The magnetic susceptibilities of the com-

plexes were determined by the Gouy method. The magnetic

field was produced by means of a Varian Associates Model

V-4004, 4" electromagnet equipped with 4" cylindrical

pole pieces. The magnet was used in conjunction with a

Varian Associates Model V-2300-A power supply and a Varian

Associates Model V-2301-A current regulator, which was

used to maintain constant current (+ 1 x 10-3 amp).

The 4" pole pieces, separated by a 2-1/4" air gap,

gave a maximum field strength of 6,800 gauss. The magnetic

field was calibrated by using standard solutions of

nickel(II) chloride, water, and solid nickel ammonium

sulfate-6-hydrate.*

TemDorature control.--The tcr: naturee control

apparatus followed the basic design of Figgis and Nyholm

(15) and Clevenger (3).


See Appendix I.











To determine the period of time required for the

sample to reach thermal equilibrium after the cryostat had

attained the desired temperature, the force acting on the

sample was measured at five minute intervals until the

measured force became constant. It was determined that

between thirty and forty-five minutes were required for the

sample to reach thermal equilibrium within the cryostat.

Cryostat.--The cryostat used was a pyrex model

following the basic design of Figgis and Nyholm (15) and

Clevenger (3).

Samole tube.--A quartz sample tube, approximately

3.5 mm. inside diameter, was fitted with a tapered teflon

stopper. The tube was suspended in the cryostat, from the

balance, by a gold chain. The sample tube was calibrated

for a volume of 2 ml. by using water delivered from a

calibrated T.D. pipette. The position of the meniscus

was marked by etching with hydrogen fluoride. The sample

tube was approximately 18.6 cm. in length, so that the

sample might extend from the region of maximum field

strength to a region of negligible field strength. A

quartz sample tube was used so as to eliminate the large

paramagnetism which was obtained with the pyrex sample

tubes. The _all diamagnetic correction for the quartz

tube wLa determined as a function of temperature.*


~cc; f)er.c~ix ii.










Balance.--A Mettler Model B-6 semi-micro balance of

0.01 mg. sensitivity was used to measure the force exerted

by the magnetic field upon the sample.

Conductivity measurements.--All conductances were

measured using an Industrial Instruments Inc. Model RCM

15 Bl Serfass Conductivity Bridge and a cell with a cell

constant of 1.4659 cm- All measurements were made at

250C. in absolute ethanol, and in tetrahydrofuran, using

10-3 M solutions. A silicone oil bath, regulated by a

Sargent Thermonitor, Model SW, was used to maintain

constant temperature.

Molecular weight determinations.--A Mechrolab Model

302 Vapor Pressure Osmometer, with tetrahydrofuran as the

solvent, was used to determine the molecular weights of

the complexes.

Spectrophotometer.--A Cary Model 14 Recording

Spectrophotometer was used to determine the ultra-violet,

visible and near infrared solution spectra of the complexes.

A Cary Model 1411 Diffuse Reflectance Accessory was

employed to determine the solid state spectra of the com-

plexes. A Perkin-Elmer Corporation Model 21 Recording

Infrared Spectrophotometer was used to determine the

infrared spectra of the complexes.











RESULTS

Magnetic Data


The complexes that were prepared, isolated and

identified are bis-[2-(apyridylmethyleneaminomethyl)-

pyridine]cobalt(II) chloride, bis-[2-(a-pyridylmethylene-

aminomethyl)pyridine]nickel(II) chloride, dichloro-2-(a-

pyridylmethyleneaminomethyl)pyridineiron(II), and chloro-

2-(a-pyridylmethyleneaminomethyl)pyridinecopper(II)

chloride. The magnetic moments of these complexes

determined at room temperature and two different field

strengths are reported in Table 1.


Complex


[Fe(PMP)C1l

[Co(PMP)2]
[Ni(PMP)2C

[Cu(PMP)Cl]


TABLE 1

MAGNETIC MOMENTS AT 2990K
a
Peff )
(B.M.) (]

,]c 5.49
C12 4.63

)12 3.08

C1 2.15


aField Strength = 6,770 Gauss.
bField Strength = 5,860 Gauss.
CThe ligand 2-(a-pyridylmethyleneaminomethyl)-
pyridine is abbreviated as PMP.
11


b
feff
B.M.)

3.11

4.63

3.08

1.98










The magnetic susceptibility of each complex was

determined as a function of temperature (from approximately

90K to the sample decomposition temperature), and were

found to exhibit normal temperature dependence (Figures

1,2,3,4). A Curie constant, C, and a Weiss constant, 9,
which were evaluated for each complex, are reported in
Table 2.


TABLE 2

CURIE AND WEISS CONSTANTS FOR NORMAL
DEPENDENT COMPLEXES


TEMPERATURE


Complex


[Fe(PMP)C1l2]

CCo(PMP)2]C12

[Ni(PMP)2]C12

[Cu(PMP)C13C1


C @o


1.58 11.53

2.64 20.60

1.30 16.20

.672 35.62


Pa = 2.84 VC

The susceptibilities were corrected for the dia-

magnetism of the ligands and metal ions (40)+ and are re-

ported, together with the corresponding magnetic moments
and temperatures, in Tables 3, 4, 5 and 6.



Field Strength 6,770 Gauss.
+See Appendix III.


Pa
(3.M.)

3.57

4.70

3.25

2.33


Po at 2990K
(3.M.)

3.49

4.63

3.08

2.15
















1.70



1.50-


0
"1.30




1.10-



.90o
800 1600 2400 3200 4000
TOK

Fig. l.--Temperature dependent susceptibility of [Fe(PMP)C12]











1.50


1.30-



1.10



.90



.70



.50
800


1600 2400 3200 4000
TK

Fig. 2.--Tomperature dependent susceptibility of [Co(PMP)2]C12











3.10-
0


2.70



2.30




S1.90



1.50



1.10I_
800 1600 2400 3200 4000
TK

Fig. 3.--Temperature dependent susceptibility of [Ni(PMP)2]C12










8.00



7.00



6.00



5.00



4.00



3.00


1600 2400 3200 4000
TK

Fig. 4.--Temperature dependent susceptibility of [Cu(PMP)Cl]C1









TABLE 3
VARIATION OF MOLAR SUSCEPTIBILITIES AND MAGNETIC
MOMENTS OF [Fe(PMP)C12] WITH TEMPERATURE


ToK )c x 106 effa Peffb
(c.g.s.units) (B.M.) (B.M.)
129.8 11245 3.40 3.11
146.2 10105 3.45 3.17
167.7 8900 3.47 3.17
189.1 7920 3.46 3.22
212.2 7100 3.48 3.21
228.6 6655 3.51 3.26
250.1 6070 3.50 3.28
271.5 5575 3.49 3.27
300.2 5105 3.51 3.30
319.4 4790 3.52 3.30


aField
bField


Strength = 6770 Gauss
Strength = 5860 Gauss









TABLE 4

VARIATION OF MOLAR SUSCEPTIBILITIES AND MAGNETIC
MOMENTS OF CCo(PMP)2]C12 WITH TEMPERATURE


TOK )Cc x 106 Peff
(c.g.s.units) (B.M.)
124.6 19816 4.49

139.7 18370 4.54
160.2 16251 4.58
181.8 14572 4.62
206.8 12889 4.64
227.6 11677 4.62
299.1 9160 4.70

336.3 8147 4.70
354.1 7744 4.70

571.3 7193 4.64
397.0 7004 4.73









TABLE 5
VARIATION OF MOLAR SUSCEPTIBILITIES AND MAGNETIC
MOMENTS OF [Ni(PMP)2]C12 WITH TEMPERATURE


TOK Xc x 106 Peff
(c.g.s.units) (B.M.)
125.1 8981 3.01
145.2 7896 3.04
170.4 6841 3.07
193.5 6103 3.08
211.8 5664 3.11
256.8 5156 3.14
257.6 4706 3.13
296.2 4060 3.11
518.0 3822 3.13
341.3 3568 3.14
364.7 3317 3.12
387.0 3159 3.13










TABLE 6

VARIATION OF MOLAR SUSCEPTIBILITIES AND MAGNETIC
MOMENTS OF [Cu(PMP)C1]C1 WITH TEMPERATURE


166.3

192.7

221.4

246.5

273.9

296.9

318.5

340.0
aField
bField


Xc x 106
(c.g.s.units)

3240

2900

2600

2365

2200

2005

1860

1775

Strength = 6770
Strength = 5860


a
Peff
(B.M.)

2.08

2.12

2.15

2.17

2.21

2.19

2.19

2.20


b
Peff
(B.M.)

1.91

1.96

2.01

2.02

2.04

2.04

2.06

2.06


Gauss
Gauss











Conductivity Data


The specific conductance of each complex, which was
determined at 250C, is reported in Table 7. The conductance
values for the cobalt(II) and nickel(II) complexes are
within the range of those expected for complexes of the

type [ML2]C12. The data for the copper(II) complex
indicate that it is of the type [CLC1]CI. The iron(II)

complex is indicated to be of the type [MLC12]. The low
conductivity of this complex probably results from a

solvation reaction in which the chloride ions undergo a

slight dissociation.

TABLE 7
SPECIFIC CONDUCTANCES AT 250C

Complex Concentration
(moles per liter) (ohm cm. )

[Fe(PP)C12] 1 x 10-3 20.9a 4.3b

[Co(PXP)2]C12 1 x 10-3 44.7 36.8

i(?2)2]C1 1 1 10~ 42.1 39.2

:Cu(P2)C1]Cl 1 x 10~ 31.7 19.4


abthanol Solution.
S-.trrc:yirofurnn Solution.
Lea Appendix IV.











Iclecular Weight Determinations


The values determined for the cobalt(II) and

nickel(II) complexes are within the range of those

expected for complexes of the type [ML2]C12. Despite the

low solubility of the iron(II) and copper(II) complexes in

--trahydrofuran, the values found indicate that these

species are uni-molecular, in solution, with only one

tridentate ligand, PMP, around each metal ion. The values

are reported in Table 8.*

TABLE 8

KOLEC-LAR WEIGHS

Values (a.m.u.)
Complex Calculated Observed

[Fe(PX.P)2C1]a 324 300

?Co(P?)2 3C12b 524 550

[Li(P:?)2]C12b 524 560

[Cu(P::P)C1]Cla 332 350


Soectrosconic Data

2~' results from tha spectral measurements are re-

.c-sca in tables 9, 13, 11, 12, and 13.

SCnconrat.ion = .Cm.
3oncenr-rtion =C.
See Appendix V.










TABLE 9
ABSORPTION MAXIMA AND MOLAR EXTINCTION COEFFICIENTS
DETERMINED FROM THE ULTRA-VIOLET SPECTRA OF LIGAND
AND COMPLEXES


Wavelengths Concentrations Molar Ex-
(angstrom units) (moles per liter) tinction
Coefficients
PMP

2450 2 x 10-* 8.5 x 103

[Fe(PMP)C12]
2665 1 x 10-4 1.2 x 104

[Co(PMP)2]Cl2
2475 1 x 10- 7.7 x 10l
2560 1 x 10-4 9.6 x 103
[Ni(PMP)2]C12
2500 1 x 10-4 4.4 x 103
2620 1 x 10-4 9.5 x 103

[Cu(PMP)Cl]C1
2500 1 x 10-4 2.0 x 104
2900 1 x 10-4 1.5 x 10
Not isolated from solvent.










TABLE 10

ABSORPTION MAXIMA AND MOLAR EXTINCTION COEFFICIENTS
DETERMINED FROM THE VISIBLE SPECTRA OF LIGAND AND
COMPLEXES


Wavelengths Concentrations Molar Ex-
(angstrom units) (moles per liter) tinction
Coefficients


PMP

3750
[Fe(PMP)C12]

3520
4800

5750
[Co(PMP)2]C12

5175

5550
[Ni(PMP)2]C12

5800
[Cu(PMP)Cl]Cl

3730
3900

5050
Not isolated.


1 x 10-2*


10-4
10-


10-5


10-2

10-2


1 x 10-2


1 x 10-3
1 x 10-3

1 x 10-3
from solvent.


1.4 x 102


1.5 x

1.3 x


1.2 x 102










TABLE 11
ABSORPTION MAXIMA DETERMINED FROM THE SOLID STATE
VISIBLE SPECTRA OF THE COMPLEXES

Wavelengths
(angstrom units)
[Fe(PMP)C12]
4850
5900

[Co(PMP)2]C12
5100
5500

[Ni(PMP)2]C12
4450

5750

]Cu(PMP)Cl]Cl

5050







26

TABLE 12

ABSORPTION MAXIMA DETERMINED FROM THE SOLID STATE
NEAR INFRARED SPECTRA OF THE COMPLEXES

Wavelengths
(angstrom units)

[Co(PMP)2]Cl2

10600

[Ni(PMP)2]C12

8100

9700








TABLE 15

INl2:''-LD A.SL I2ION BANDS (cm.-1) FOR 2-(a-PYRIDYLMETHYLENEAMINOMETHYL)-PYRIDINE
AND ITS COMPLEXES


Assi ~'r-ent Pi

st CH 282'
294
st C=N 1651
acrylic )
Bond I 159
(py ring)
Basnd II 156
(py ring)
Band III 146
(py ring)
Band IV 142
(py ring)
d CH 115
(py ring) 103

75
77


;1p

3 v
5 vi
0m

0 s

0 (:

0 s

0 s

0 s
7s

4m
2m


sh)


(b)


[Fe(PMP)C12]

2875 vw
2995 vw



1595 s

1562 (sh)

1458 s

1424 s

1147 s
1045 s

757 m(b)


[Co(PMP)2]C12

2875 vw
2950 vw
1627 m

1595 s

1562 (sh)

1471 s

1428 s

1137 s
1044 s
747 m
772 m(b)


[Ni(PMP)2]C12

2940 vw
2975 w
1645 m

1585 s

1562 (sh)

1462 s

1425 s

1142 s
1042 s

747 m
772 m(b)


[Cu(PMP)C1]C1

2880
2998
1648 m

1588 s

1562 (sh)

1462 s

1424 s

1143 s
1042 s


772 (sh)


--- c
-`----


-------












DISCUSSION


A number of complexes formed between iron(II),

cobalt(II), nickel(II) and copper(II) and tridentate

ligands containing the basic terpyridine linkage have

been prepared by Lions and coworkers (11,16,17,27). Many

of the ligands formed bis-tridentate complexes with the

metal ions, i.e., six-coordination compounds of the type

[ML2]C12. However, some ligands, e.g. 2-methyl-8-(6 -

methyl-a-pyridylmethyleneamino)quinoline, formed only

one-to-one complexes with copper(II) of the type

[CuLC1]C1, and completed not at all with iron(II), while

others formed complexes of iron(II), cobalt(II), nickel(II)

and copper(II) of the type [MLC12], in which the ligands

are assumed to function as bi- or tridentates, with four-

or five-coordination. The existence of polymeric

structures in the solid state has not been definitely

precluded.

During the present investigation complexes of

iron(II), cobalt(II), nickel(II) and copper(II) with the

tridentate ligand, 2-(a-pyridylmethyleneaminomethyl)-

pyridine (PMP), were prepared and studied. This ligand

contains the basic terpyridine linkage, -N=C-C=N-C-C=N-.










It has been definitely proven that, in the case of the

cobalt(II) and nickel(II) complexes, two of the tridentate

ligands (PMP) are coordinated to each metal ion, forming

six-coordinate complexes. The stereochemistries of the

iron(II) and copper(II) complexes are not definitely

assigned.

The cobalt(II) complex, ECo(PMP)2]C12, was found

to have a room temperature magnetic moment of 4.63 B.M.

Spin-free octahedral cobalt(II), a d7 ion, has a 4Tlg
-g
ground state, which provides an orbital contribution to

the magnetic moment. The value of the magnetic moment

expected, based on this ground state, is 4.1 B.M. The

larger value observed, which is in accord with the

magnetic moments of many high-spin octahedral cobalt(II)

complexes, can be explained on the basis of spin-orbit

coupling which mixes in some of the higher levels having

orbital angular momentum with the ground state.
8 h 3
Octahedral nickel(II), a d8 ion, has a Ag ground

state which provides no orbital contribution to the mag-

netic moment. The magnetic moment expected on the basis

of this ground state is 2.8 B.M. The observed value,

3.08 B.M., is justified by the existence of higher levels
having orbital angular momentum that can be mixed with the

ground state via the mechanism of spin-orbit coupling.










The copper(II) complex has a room temperature

magnetic moment of 2.15 B.M. This complex was found to be

field strength dependent in that as the field strength was

decreased, the value of the magnetic moment also decreased,

thus indicating some form of metal-to-metal interaction.

Analytical data indicate that the complex is either

four- or five-coordinate. The low conductances make it

extremely difficult to determine whether the complex is of

the type [MLC1]C1, i.e. four-coordination with one chloride

ion outside of the primary coordination sphere, or of the

type C[LC12], i.e. five-coordination with the conductivity

values being due to a solvation reaction in which some of

the chloride ions are replaced by solvent molecules.

Because of the propensity of copper(II) complexes toward

square-planar four-coordination and because of the

existence of similar compounds prepared by Lions (17),

this complex is assumed to be four-coordinate square-planar.

The metal-to-metal interaction could possibly arise

t -2ough a direct copper-to-copper coupling mechanism, as

in the copper(II) acetate complex (13), but ligand steric

effects make this seem unlikely. A copper-to-chloride-to-

copper coupling, a super-exchange phenomenon analogous to

that found in systems such as FeO, CoO, or XnO, cannot be

definitely excluded here.










A similar problem arises in the interpretation of

the magnetic and analytical data of the iron (II) complex.

High-spin octahedral iron(II) complexes normally have

magnetic moments around 5.1 B.M., while the low-spin

systems have moments around .5 B.M. The only four-

coordinate square-planar iron(II) complex that has been

well characterized is the phthalocyanine complex, which

has a room temperature magnetic moment of 3.96 B.M. The

room temperature magnetic moment of the iron(II) complex

presently being studied was found to be 3.49 B.M. and is

also field strength dependent. With the analytical data

indicating four- or five-coordination, it is difficult to

make a plausible stereochemistry assignment. If the

complex is assumed to be four- or five-coordinate in

solution, it could conceivably increase its coordination

number to six in the solid state through the formation of

chloride bridges, at the same time providing a mechanism

for metal-to-metal interaction. However, this cannot be

definitely concluded and the question must remain open.

For the cobalt(II) complex in solution, four ab-

sorption bands were observed: two in the ultra-violet

region, at 2,475 A and 2,560 A, which were assigned to

electronic transitions on the ligand, and two in the visible

region, at 5,175 A and 5,550 A. In the solid state three

absorption bands were observed: two in the visible region,










at 5,100 A and 5,500 A, and one in the near infrared region,

at 10,600 A. The absorption maximum at 10,600 A (9,450 c-~1)

is assigned as the T (?) --> T2(F)transition, thus

giving a value of 1180 cm.-1 for D The absorption in the

visible region from the solid state spectra and the solution

spectra are assumed to arise from the same transitions.

Thus the absorption at 5,500 A (18,200 cm.-l) is assigned as

the lg(F) ---> A 2g(F) transition and the absorption at

5,100 A (19,600 cm.-1) is assigned as the 4T g(F) -
4g
4 g(P) transition (Figure 5).




g2g
4 -------------



4,

-2g



-2g





3.. tric Cctahedral Tetragonal
7ield Field Field

?i.5 5.-- nrr states which arise from the aFnd
? tr- states of a c ion in a regular and tetragonally
iistor-ted octahedral-field.









Using the value of q determined from the T l(F) -
4T2g(F) transition, the absorption values for the transi-

tions g (F) --> 42g(F) and 4Tg(F -> T(P) are
calculated to be, respectively, 4,700 A (21,300 cm.-1) and
4,450 A (22,500 cm.- ). These calculations are based on
transitions for regular octahedral complexes and no allow-
ances are made for tetragonal distortion. Thus the validity
of the assignments is not questioned because of the dis-
crepancies between the calculated and observed values.
Indeed, the absorption at 5,500 A agrees closely with that
found at 5,530 A in the [Co(terpy)3 ]++ complex and assigned
as the 4Tlg(F) -> 42(F) transition (19).
From the solution spectra of the nickel(II) complex

three absorptions were observed: two in the ultra-violet
region, at 2,500 A and at 2,620 A, which were assigned as
charge-transfer bands, and one in the visible region at

5,800 A (17,500 cm.-1). From the solid state spectra four
absorptions were observed: two in the visible range, at
4,450 A (22,500 cm.-1) and at 5,750 A (17,400 cm.-1), and
two in the near infrared region, at 8,100 A (12,350 cm. )
and at 9,700 A (10,300 cm.-1). The band at 5,750 A from
the solid state spectra and the band at 5,800 A from the

solution spectra are assigned as the same transition.
If the absorption at 8,100 A is assigned as the

3 2g(F) --> T2g(F) transition, then a value of 1,235 cm.-1










is found for D The maximum at 9,700 A is assigned as
the A 2g(F) ---> (D) transition, while the band at

5,800 A is assigned as the 2g(F) 3ilg(F) transition.
These observed values are only slightly lower than those of

the [Ci(dipy) 3]+ and [Ni(terpy)2]++ complexes (1,19,34).

The absorption maximum at 4,450 A could only be tenuously

assigned to the 3A2g(F) -- Tlg(P) transition (Figure 6).



13,









10 D
-q


Fig. 6.--Partial energy level diagram for a d8 ion
in an octahedral field, showing the triplet states and the
lowest singlet state.


From the spectra of the iron(II) complex six
absorptions were observed: one at 2,665 A, from the ultra-

violet solution spectra, and assigned as an electronic

transition on the ligand; three from the visible solution








35

spectra, at 3,520 A (28,400 cm.-1), at 4,800 A (20,800 cm.-1)
and at 5,750 A (17,400 cm.-l); and two from the solid state
visible spectra, at 4,850 A (20,600 cm.-1) and at 5,900 A
-1
(16,950 cm. ). The absorptions at 4,800 A from the
solution spectra and 4,850 A from the solid state spectra
were assigned as the same transition. There is some doubt
as to whether the absorptions at 5,750 A from the solution
spectra and 5,900 A from the solid state spectra arise from
the same transition. In the absorption spectra of the

[Fe(H20)6]++ complex, a band composed of two maxima is
found at 10,000 cm.-1 and 12,000 cm.-1, which is identified

as the 5T (D) -> 5E (D) transition (Figure 7), split
-2g g
because of a Jahn-Teller effect (21,26). Since the ligand
field of PMP is greater than that of water, the absorptions

are expected to occur at higher values. Thus the absorp-

tions at 5,750 A and 5,900 A are tentatively assigned as
the 5T(D) -> 5E (D) transition, while the remaining
2g -g
peaks are supposedly the transitions T2g(D) --> lg(D),

T 2g(D),... These are not identified with certainty, in
part because of the indefinite assignment of the stereo-


chemistry of the complex.












3H 3T
2g




5
-E






-g
5 / 5 5E
"'-- --2g -.




Symmetric Octahedral Trigonal
Field Field Field

Fig. 7.--Energy states which arise from the 3H and
D term states of a d6 ion in a regular and trigonally
distorted octahedral weak field.


For the copper(II) complex in solution, five
absorption bands were observed: two in the ultra-violet
region, at 2,500 A and 2,900 A, which were assigned as
electronic transitions on the ligand, and three in the
visible region, at 3,730 A (26,800 cm.-1), 3,900 A
(25,600 cm.-1) and at 5,050 A (19,800 cm.-1). In the
solid state spectra one absorption band was observed at

5,050 A and this band and the band from the solution
spectra at 5,050 A are assigned as the same transition.








37

From the spectra of [Cu(dipy) ]++ a band is reported
at 14,700 cm.-1 (22), while a slightly lower value is

reported from the [Cu(terpy)2]++ spectra (19,22). No

absorptions in this region were observed from the spectra

of the copper(II) complex presently being studied. Because

of the Jahn-Teller effect, no regular octahedral copper(II)
complexes are expected to exist (33) and, indeed, it is

generally found that the E and 2 levels are split
-g 2glit
into two components each (Figure 8), which give rise to

three transitions (10,12,20). On this basis the absorptions

observed in the visible region of the spectrum are assigned

as transitions 2Blg 2 A E2g This is in
agreement with the proposed four-coordinate square-planar

configuration of the copper(II) complex.

2g


NT -2 2
22T 2

B2 ..g

2 2
-g, -Ig

2

Symmetric Octahedral Tetragonal
Field Field Field

Fig. 8.--Energy states which arise from the 2D term
otate of a d ion in a regular and tetragonally distorted
octahedral field.








38

The present investigation of these complexes

suggests a number of areas in which future work must be

done before a better understanding of the magnetic and

spectral behavior of iron(II) and copper(II) complexes can

be gained. The magnetic susceptibilities of these com-

plexes in solution, and the magnetic properties of single

crystals, should be thoroughly investigated. A detailed

x-ray diffraction study should be made. There is a tre-

mendous amount of work yet to be done in connection with

spectral characterizations, especially those of iron(II)

complexes.












SUMMARY


The syntheses of the iron(II), cobalt(II), nickel(II)

and copper(II) chloride complexes of the tridentate ligand

2-(a-pyridylmethyleneaminomethyl)pyridine (PMP) are

reported. The cobalt(II) and nickel(II) complexes are

six-coordinate and of the type [ML2]C12 while the iron(II)

and copper(II) complexes, in solution, are presumed to be

four- or five-coordinate, that is [MLC1]C1 or [MLC12].

The solid state magnetic susceptibility of each of

these complexes was determined as a function of temperature.

It was demonstrated that each of the complexes follows the

Curie-Weiss law, but that the magnetic moment of the

iron(II) and copper(II) complexes were found to be field

strength dependent. The room temperature magnetic moments

of the cobalt(II) and nickel(II) complexes are those

expected for high-spin octahedral complexes whereas the

moment exhibited by the copper(II) complex was that

expected for either a square-planar or an octahedral

complex. The moment exhibited by the iron(II) complex is

consistent with neither of these stereochemistries and

indicates a significant degree of metal-to-metal inter-

action.







40

Definite assignments were made for the absorptions

of the cobalt(II), nickel(II) and copper(II) complexes in

the ultra-violet, visible, and near infrared regions of

the spectra. Only tentative assignments could be made for

the absorption maxima of the iron(II) complex. These

assignments correspond to Dq values that are within the

range expected for complexes formed by these ions with

terpyridine-like ligands. Definite assignments of the

iron(II) complex are difficult because of the uncertainty

surrounding its stereochemistry.












BIBLIOGRAPHY


1. A. Abragam, J. Horrowitz and J. Yvon, Rev. Mod. Phys.
25, 165(1953).

2. C. J. Ballhausen, "Introduction to Ligand Field Theory"
(McGraw-Hill Book Company, Inc., New York, 1962).

3. E. A. Clevenger, "Anomalous Magnetic Behavior of Some
Six-Coordinate Cobalt(II) Complexes," Thesis,
University of Florida, 1961.

4. P. Cossec, J. Inorg. and Nuclear Chem. 14, 127(1960).

5. F. A. Cotton and R. H. Holm, J. Chem. Phys. 52, 1168
(1960).
6. F. A. Cotton and R. H. Holm, J. Am. Chem. Soc. 82,
2979(1960).
7. F. A. Cotton and R. H. Holm, J. Am. Chem. Soc. 82,
2983(1960).

8. F. A. Cotton, J. Am. Chem. Soc. 83, 1780(1961).

9. P. Curie, Ann. chim. et phys. 5, 289(1895), et seq.
10. J. D. Dunitz and L. 3. Orgel, "Advances in Inorganic
and Radiochemistry," 2 (Academic Press, Inc., New York,
1960). pp. 1-60.

11. F. P. Dwyer, N. S. Gill, E. C. Gyarfas and F. Lions,
J. Am. Chem. Soc. 75, 3834(1953).
12. A. Earnshaw and J. Lewis, Nature, Lond. 181, 1262(1958).

13. B. N. Figgis and R. L. Martin, J. Chem. Soc., 3837(1956).
14. B. N. Figgis, Nature 182, 1568(1958).

15. B. N. Figgis and R. S. Nyholm, J. Chem. Soc., 331(1959).
16. J. F. Geldard and F. Lions, Inorg. Chem. 2, 270(1965).

17. H. A. Goodwin and F. Lions, J. Am. Chem. Soc. 81, 6415
(1959).









18. J. S. Griffith and L. E. Orgel, Quart. Revs. 11,
581(1957).
19. R. Hogg and R. G. Wilkins, J. Chem. Soc., 341(1962).
20. 0. G. Holmes and D. S. McClure, J. Chem. Phys. 26,
1686(1957).
21. E. K. Jorgensen, Acta Chem. Scand. 8, 1502(1954).
22. E. K. Jorgensen, Acta Chem. Scand. 9, 1362(1955).
23. E. K. Jorgensen, J. Inorg. and Nuclear Chem. 1, 501
(1955).
24. H. Kambe, J. Phys. Soc. Japan 5, 48(1950).
25. J. Lewis and R. G. Wilkins, eds., "Modern Coordination
Chemistry" (Interscience Publishers, Inc., New York,
1960). pp. 229-300, pp. 400-478.
26. A. D. Liehr and C. J. Ballhausen, Ann. Phys. (N.Y.) 2,
304(1958).
27. F. Lions and K. V. Martin, J. Am. Chem. Soc. 79,
2733(1957).
28. G. Maki, J. Chen. Phys. 28, 651(1958).
29. R. S. Nyholm, Quart. Revs. 7, 577(1953).

50. L. E. Orgel, J. Chem. Soc., 4756(1952).
31. L. E. Orgel, J. Chem. Phys. 23, 1819(1955).
32. L. E. Orgel, Report to X Solvay Council, Brussels
(1956).
55. L. E. Orgel and J. D. Dunitz, Nature 179, 462(1957).
34. H. A. Robinson, J. D. Curry and D. H. Busch, Inorg.
Chem. 2, 1178(1963).

35. L. Sacconi, G. Lombardo and R. Ciofalo, J. Am. Chem.
Soc. 82, 3487(1960).

36. P. W. Selwood, "Magnetochemistry" (Interscience Pub-
lishers, Inc., New York, 1956). pp. 91-97.







43

37. C. G. Shull, W. A. Strauser and M. K. Wilkinson, Rev.
Mod. Phys. 25, 100(1953).

38. L. E. Sutton, J. Chem. Ed. 37, 498(1960).

39. J. H. Van Vleck, "Theory of Magnetic and Electric
Susceptibilities" (Oxford Univ. Press, London, 1932).

40. J. H. Van Vleck, Phys. Rev. 41, 208(1932).

41. A. Werner, Z. anorg. Chem. 3, 267(1893).

42. A. Werner, "Neure Anschaungen auf den Gebiete der
anorganischen Chemi," translated by Headly (Longman,
Green and Company, New York, 1911).





























APPENDICES











APPENDIX I
Calibration of Field Strength as a Function of Current

The strength of the magnetic field was standardized
by using a 29 per cent NiC12 solution, water, and solid
nickel ammonium sulfate-6-hydrate. The gram susceptibility
of the NiC12 solution is dependent on the mole function of
NiC12 in the solution (36):



Xg [10 0 p + 0.720(1-p)] x 10-6 erg gauss-2

The susceptibility of the water is reported to be
0.72 x 10-6 erg gauss-2(36) andX for Ni(NH4)2(S04)2"6H20
is reported to be (4)


C[ 1742 0.50) x 10-6 erg gauss-2
T+2.ggas










TABLE 14

FIELD STRENGTH AS A FUNCTION OF CURRENT
AS DETERMINED WITH WATER

Amperage H
(gauss)

4.0 6693

5.8 6504
3.6 6558

3.4 6558

3.2 6140
5.0 5950

2.8 5577
2.6 5157

2.4 4879

2.2 4775

2.0 4123










TABLE 15

FIELD STRENGTH AS A FUNCTION OF CURRENT AS DETERMINED
WITH NICKEL AMMONIUM SULFATE-6-HYDRATE

Amperage H
(gauss)
4.0 6848

3.8 6656

3.6 6458

3.4 6253

3.2 6025

3.0 5771
2.8 5459

2.6 5148

2.4 4848

2.2 4461

2.0 4123










TABLE 16

AVERAGE FIELD STRENGTH AS A FUNCTION OF CURRENT

Amperage H
(gauss)

4.0 6770

3.8 6580

3.6 6508

3.4 6405

3.2 6082

3.0 5860

2.8 5518

2.6 5152

2.4 4863

2.2 4618

2.0 4123










APPENDIX II

TEMPERATURE DEPENDENT DIAMAGNETIC CORRECTIONS
FOR A QUARTZ GOUY TUBE

Several quartz Gouy tubes were prepared and found

to be slightly diamagnetic. The following data were

obtained by using a magnetic field of approximately 6770

gauss.

TABLE 17

TEMPERATURE DEPENDENT DIAMAGNETIC CORRECTIONS
FOR A QUARTZ GO-UY TUBE

TK 1/T x 103 A

88.04 11.36 -0.00513

100.24 9.98 -0.00285

148.84 6.72 -0.00270

177.54 5.65 -0.00268

221.44 4.52 -0.00271

314.64 3.18 -0.00269

359.40 2.78 -0.00270











APPENDIX III


The complexes were corrected for diamagnetism by

using Pascal's constants.


TABLE 1

PASCAL'S CORRECTIONS

C6H5
C6H5N

C

N (open chain)

C1

C=N

H

0

Fe

Co

Ni

Cu


FOR DIAMAGNETISM

-55.5 x O16 c.g.s

-49.2

- 6.0

- 5.6

-20.1

8.2

2.9

4.6

-12.8

-12.8

-12.8

-12.8











APPENDIX IV


Conductances of certain compounds were determined

in tetrahydrofuran solution and used as standards.


TABLE 19

SPECIFIC CONDUCTANCES AT 250C


Concentration
(moles per liter)

1 x 10-

1 x 10-3

1 x 10-3

1 x 10-3


(ohm- cm.- )

15.3
42.8

46.4

41.0


Compound


KC1

CoC12
MnC12

CoBr2











APPENDIX V


Molecular weights of certain compounds were deter-

mined in tetrahydrofuran solution and used as standards.


TABLE 20

MOLECULAR WEIGHTS

Compound Values (a.m.u.)
Calculated Observed

KC1 75 82

CoC12 150 145

MnC12 126 137

CoBr2 219 240












BIOGRAPHICAL SKETCH


James Leroy Petrofsky was born March 2, 1938, at

Jacksonville, Texas. After attending Pendorff Grade

School, Laurel, Mississippi, he entered Jones County

Agricultural High School, Ellisville, Mississippi, and

was graduated in May, 1955. In June, 1959, he received

the degree of Bachelor of Science from Mississippi College,

Clinton, Mississippi. In September, 1959, he entered the

Graduate School of the University of Florida and in

February, 1962, he received the degree of Master of

Science. From that time until December, 1964, he held a

graduate assistantship in the Department of Chemistry.











This dissertation was prepared under the direction

of the chairman of the candidate's supervisory committee

and has been approved by all members of that committee.

It was submitted to the Dean of the College of Arts and

Sciences and to the Graduate Council, and was approved as

partial fulfillment of the requirements for the degree of

Doctor of Philosophy.

December 19, 1964


Dean, Col3ee oj Arts and Sciences




Dean, Graduate School

Supeisory C mmittee:


Chai an




1<* ^ -/-/







































z432 a




University of Florida Home Page
© 2004 - 2010 University of Florida George A. Smathers Libraries.
All rights reserved.

Acceptable Use, Copyright, and Disclaimer Statement
Last updated October 10, 2010 - - mvs