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MECHANISMS OF AQUATION AND BASE HYDROLYSIS IN

COBALT(III) AMINE COMPLEXES

THESIS

SUBMITTED

FOR THE DEGREE OF DOCTOR OF PHILOSOPHY

IN THE

AUSTRALIAN NATIONAL UNIVERSITY

INGE

I. OLSEN

The work described in this thesis has been

completed in the Research School of Chemistry under the supervision of Dr A.M. Sargeson. Mr H. Satrapa carried out some preliminary studies of the kinetic experiments described in Part I, Chapter 2; otherwise the work is the candidate's own. 7~

November 1968.

PREFACE.

In spite of many studies of the mechanisms of

aquation and base hydrolysis reactions of cobalt (III) amine complexes there is still controversy. The work in this thesis is aimed at clarifying some of the problems and ambiguities which have arisen.

Part I of the thesis is mainly concerned with the

study of induced aquation reactions of complexes of the types [co (NH 3) 5 x] 2 +, [coen 2NH 3 x] 2 +, and [coen 2 XY J+ where intermediates of reduced coordination number supposedly are produced. These intermediates are generated by treating the complexes where X and/or Y are chloride, bromide or iodide with mercuric ion or where X and/or Y are carbamate or azide with nitrous acid. Studies of competition by other species in aqueous solution and of the stereochemistry of the reactions are used to characterize the intermediates. Also the nature of the intermediates is discussed. The results from the induced aquation reaction studies are shown not t0 agree with results obtained under similar conditions for the spontaneous aquation reactions, thus implying that the same intermediates are not formed in the two types of reactions. Part II of the thesis is concerned with the mechanism of base hydrolysis of cobalt(III) amine complexeso It is shown that when base hydrolysis of complexes of the types [co(NH 3)5 x] 2 + and [Coen 2 NH 3 x] 2 + (where Xis chloride, bromide, iodide or nitrate) takes place in the presence of added anions some products are obtained with the competing ion incorporated. This result combined with the fact that constant competition ratios and constant stereochemistry are observed for different complexes under identical conditions is used to support a mechanism which involves a common five-coordinate intermediate for each type of complex. The nature of the intermediates is discussed in the last chapter of the thesis. The work has been carried out under the supervision of Dr A. Sargeson to whom the author is indebted for his encouragement and never failing readiness to discuss any problem. Dr Do Buckingham must be thanked for many valuable discussions and suggestions. The micro- analytical departments at The John Curtin School of Medical Research and at The Research School of Chemistry performed the N, C, H, and Co analysis for which the author is thankful. Valuable technical assistance was given by Messrso H. Satrapa, S. Brown and A.

Aranjelovic. The author's husband, Roger Creaser,

kindly helped with the proof reading. Finally the Australian National University is thanked for the award of a research scholarship and travel allowance.

The following papers have been published:

The Mechanism of Substitution Reactions of

Pentaamminecobalt(III) Complexeso Product Distribution in the Induced Aquation of Some [co(NH 3)5 x] 2 + Ions in the Presence of Added Anions. DoA. Buckingham, I.I.

Olsen, A.M. Sargeson, and H. Satrapa

9

Inorg. Chem.,

The Nature of the Intermediate Generated in the Catalysed

Aquation of Some [co(NH

3)5 x] 2 + Ions. D.A. Buckingham,

I.I. Olsen, A.M. Sargeson, Aust. J.Chem.

1

20, 597 (1967).

The Induced Aquation Reactions of the Resolved

Azidochlorobis(ethylenediamine)cobalt(III) Ion.

D.A. Buckingham, I.I. Olsen, A.M. Sargeson, Inorg.Chem., Mechanism of Base Hydrolysis of Some Acidopentaammine cobalt(III) Complexeso D.A. Buckingham, I.Io Olsen,

A.M. Sargeson, J.Am.Chem.Soc., 88, 5443 (1966)~

.Base Hydrolysis of [co(NH 3)5 x] 2 + Ionso DoA. Buckingham, I.I. Olsen, A.M. Sargeson, Inorg.Chemo? 7, 174 (1968).

The Stereochemistry of the Base Hydrolysis of

trans-[Co( H 3)4( 15 NH 3 )x] 2 + Ions~ DoAo Buckingham, I.I. Olsen, A.M. Sargeson, J~Am.ChemoSoco, 89, 5129 (1967). The following paper has been accepted for publication: Competition Studies and the Stereochemistry for the

Base Hydrolysis and Induced Aquation of Some

Acidoamminebis(ethylenediamine)cobalt(III) Ionso

D.A. Buckingham, I.I. Olsen

9

A.M. Sargeson, J.Am.Chem.

Saco

List of Abbreviations~

Some abbreviations used in this thesis are:

en DMSO d 6 -DMSO PY S-pic Y-pic dipy OAc trien cyclam d 4 -cyclam ethylenediamine dimethyl sulphoxide -hetadeuterio-dimethyl sulphoxide pyridine

S-picoline

Y -picoline

2~2 9 -bipyridyl acetate triethylenetetramine l,4,8,ll-tetra-azacyclo tetradecane

NNVN"N"'-tetradeuterio

cyclam

Chapter 1.

CONTENT So

Part I.

Mechanism of Aguation Reactions i~

Cobalt (III) Amine Complexeso

Introduction to Part I .

. Chapter 2.

The Mechanism of Aquation Reactions of Some

[co(NH 3)5 x] 2 + Complexes

2.1 Introduction

2.2 Experimental Section

Preparations of [co(NH

3)5 c1](c10 4)2, [co(NH 3)5

Br](c10

4)2, [co(NH 3)5 I] (c104)21 [co(NH3)50CONH2](c104)2, l Page 1 17 18 and [co(NH 3)5N3 ](c10 4)2 18

Kinetic studies of the aquation of

19

Kinetic studies of the nitrosation of

20 ii Page

Competition studies 20

Determination of equilibrium constants 22

Determination of pKa for [co(NH

3)5-

0CONH2] ( c10

4 )2

2.J Results

2.4 Discussion

Chapter J.

The Nature of the Intermediate Generated

in the Induced Aquation of Some [co(NH 3) 5 x] 2 + Ions

J.l Introduction

Jo2 Experimental Section

Deuteration and aquation

JoJ

Results

Jo4 Discussion

Chapter 4o

The Induced Aquation Reactions of Some

[Coen 2

XY]n+ Complexes

4al Introduction

4.2 Experimental Section

22
2J J2 42
4J 44
45
48
49
II II !I II II I! ii II II II II II 11 ii ii II YI II II II II 11 II II trans-[Coen 2 (N 3)2 ]c10 4 trans-[Coen 2N3 c1Jc10 4 589
-[coen 2N3 c1Jc10 4 cis-[Coen 2 DH 2N3 ]so4.H 20 t rans-[Coen2DH 2N3]- so4G2H20 589
-[coen 2 c1 2 ]c10 4 589
-[coen 2 NH 3 c1]Br 2 trans-[Coen 2 NH 3 c1Jc1c10 4 589
-[coen 2 NH 3 Br]Br 2 589
-[coen 2 NH 3No3 ]s 2o6 trans-[Coen 2 NH 3No3 ]s 2o6 589
-[coen 2 NH 3 oH 2]-

Br30H20

trans-[Coen 2 NH 3 oH 2 (No3)3 589
-[coen 2 NH 3N3 ]s 2o6 trans-[Coen 2 NH 3N3 ]s 2 o 6

NO+ induced aquations of (+)

589-
[Coen2N3c1Jc104 and (+) 589
-[coen

2(N3)2]

c104 iii P~e 50
51
52
52
53
53
53
54
54
55
56
57
57
58
iv Page Hg 2 + induced aquation of [Coen 2N 3 c1J-59 ClO 4

Spontaneous ~quation of (+)

589
-[coen 2N 3- c1Jc104 60
60
Hg 2 + induced aquation of (+) 589
-[coen 2- 60
c1 2 ]c10 4

NO+ induced aquations of trans-and

Hg 2+ induced aquations of [Coen 2 NH 3 c1]Br 29
589
-[coen 2 NH 3 Br]Br 2, and trans-[Coen 2 NH 3 c1Jc1c10 4 4oJ

Results

4.4 Discussion

61
62
6J 74

Chapter lo

Part IIo

Mechanism of Base Hydrolysis in

CobafilIII) Amine Complexeso

Introduction to Part II.

Chapter 2n

The Mechanism of Base Hydrolysi~of Some

[co(NH 3) 5 x] 2 + Complexes V Page 79

2.1 Introduction 93

2.2 Experimental Section 95

Preparation of [co(NH

3)5 No 3 ](c10quotesdbs_dbs17.pdfusesText_23