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«A Dissertation Submitted to the Graduate Faculty of the Louisiana State University and Agricultural and Mechanical College in partial fulfillment of ...»

-- [ Page 1 ] --

CHEMISTRY OF RHENIUM(I) TRICARBONYL COMPLEXES OF BIOMEDICAL

RELEVANCE

A Dissertation

Submitted to the Graduate Faculty of the

Louisiana State University and

Agricultural and Mechanical College

in partial fulfillment of the

requirements for the degree of

Doctor of Philosophy

in

The Department of Chemistry

by

Theshini Perera

B.Sc. University of Colombo, Sri Lanka, 2004

August 2010

Dedicated with love to my late mother And to my loving father ii

ACKNOWLEDGMENTS

I most sincerely acknowledge my advisor, Dr. Luigi Marzilli for his expert guidance throughout my graduate career. He has been a source of inspiration ever since our first interview and I have learnt so much these past years. I thank him for always giving me quality time and for taking out the best in me as a scientist. Dr. Pat Marzilli is gratefully acknowledged, for always being there to listen and advice and for her invaluable assistance with work in this dissertation.

I thank my committee members, Dr. Andrew Maverick, Dr. Anne Grove, Dr. Evgueni Nesterov, Dr. Martin Hjortsø and Dr. John Chandler for their support and constructive advice. I thank Dr. Frank Fronczek for the numerous crystal structure determinations, and for always being accommodative, Dr. Dale Treleaven and Dr. Thomas Weldeghiorghis for initially teaching me how to use the NMR spectrometers and for their help when needed and Dr. Malgosia Lipowska for radiolabeling of my ligands and general support.

Warm thanks go to my former lab mates, Drs Anna Maria Christoforou, Kristie Adams, Janet Manono, and Vidhi Maheshwari for initially helping me out to find my way around the lab, for all the good times we had, and the friendship; current member, Pramuditha Abhayawardhana for her friendship and cheerful support. I also thank our former postdoc, Dr Patrizia Siega, for her encouraging words and the ever smiling Ms Sherry, Kim and Deborah for their assistance.

I thank the University of Sri Jayewardenepura for granting me study leave. The support of wonderful friends has always been a blessing.

My deepest gratitude must indeed go to my parents, for bringing me up into such happiness and such love. My only sadness is that my mother is no more to see her little girl graduate, but undoubtedly, all credit should go to her and my father for a perfect upbringing in a perfect family. To my two elder brothers I express my warmest thanks for always being there for iii me and the wonderful times we had growing up. To my extended family I express my heartfelt gratitude. Finally to my husband Inoka, for everything we have shared from the start of our wonderful journey in life together, no words could ever express my appreciation for all that he has done for me.

–  –  –

DEDICATION

ACKNOWLEDGMENTS

LIST OF TABLES

LIST OF FIGURES

ABSTRACT

CHAPTER 1. INTRODUCTION

1.1. Metalloradiopharmaceuticals

1.2. fac-{MI(CO)3}+ (M = 99mTc, Re) Core

1.3. References

CHAPTER 2. NH NMR SHIFTS OF NEW, STRUCTURALLY CHARACTERIZED

fac-[Re(CO)3(POLYAMINE)]n+ COMPLEXES PROBED VIA OUTER-SPHERE H-BONDING INTERACTIONS TO ANIONS, INCLUDING THE PARAMAGNETIC [ReIVBr6]2- ANION.....6

2.1. Introduction

2.2. Experimental Section

2.3. Results and Discussion

2.4. Conclusions

2.5. References

CHAPTER 3. SEVERAL NOVEL N-DONOR TRIDENTATE LIGANDS FORMED IN

CHEMICAL STUDIES OF NEW fac-Re(CO)3 COMPLEXES RELEVANT TO fac-99mTc(CO)3

RADIOPHARMACEUTICALS. ATTACK OF A TERMINAL AMINE ON COORDINATED

ACETONITRILE

3.1. Introduction

3.2. Experimental Section

3.3. Results and Discussion

3.4. Conclusions

3.5. References

CHAPTER 4. SUPERBASIC AMIDINE MONODENTATE LIGANDS IN fac[Re(CO)3(5,5′Me2bipy)(AMIDINE)]BF4 COMPLEXES: DEPENDENCE OF AMIDINE CONFIGURATION ON THE REMOTE NITROGEN SUBSTITUENTS

4.1. Introduction

4.2. Experimental Section

4.4. Results and Discussion

4.5. Conclusions

4.6. References

v

CHAPTER 5. IMINOETHER COMPLEXES OF THE TYPE, facRe(CO)3L(HNC(CH3)OCH3)]BF4 (L = BIPYRIDINE AND SUBSTITUTED BIPYRIDINE):

SYNTHETIC, X-RAY CRYSTALLOGRAPHIC, AND NMR SPECTRAL FEATURES..........98

5.1. Introduction

5.2. Experimental

5.3. Results and Discussion

5.4. Conclusions

5.5. References

CHAPTER 6. NEW N,N,N-DONOR LIGANDS BEARING A TERTIARY SUFONAMIDO

LINKAGE. SYNTHETIC, X-RAY CRYSTALLOGRAPHIC, AND NMR SPECTRAL

FEATURES OF fac-Re(CO)3 COMPLEXES

6.1. Introduction

6.2. Experimental

6.3. Results and Discussion

6.4. Summary and Conclusions

6.5. References

CHAPTER 7. CONCLUSIONS

APPENDIX A. SUPPLEMENTARY MATERIAL FOR CHAPTER 2

APPENDIX B. SUPPLEMENTARY MATERIAL FOR CHAPTER 3

APPENDIX C. SUPPLEMENTARY MATERIAL FOR CHAPTER 4





APPENDIX D. SUPPLEMENTARY MATERIAL FOR CHAPTER 5

APPENDIX E. SUPPLEMENTARY MATERIAL FOR CHAPTER 6

APPENDIX F. PERMISSION

VITA

–  –  –

Table 2.1.

Crystal Data and Structure Refinement for [Re(CO)3(dipn)]BF4 (1), [Re(CO)3 (N′Medipn)]PF6 (2), [Re(CO)3(N,N-Me2dipn)]BF4 (3), [Re(CO)3(trenH)](PF6)2 (4), [Re(CO)3(trpnH)](PF6)2 (5), [Re(CO)3(aepn)]PF6 (6), and [Re(CO)3(tacn)]PF6 (7)

Table 2.2.

Selected Bond Distances (Å) and Angles (deg) for [Re(CO)3(dipn)]BF4 (1), [Re(CO)3(N′-Medipn)]PF6 (2), [Re(CO)3(N,N-Me2dipn)]BF4 (3), [Re(CO)3(trenH)](PF6)2 (4), [Re(CO)3(trpnH)](PF6)2 (5), [Re(CO)3(aepn)]PF6 (6), and [Re(CO)3(tacn)]PF6 (7)

Table 2.3.

Selected Non-bonded Distances (Å) [Re(CO)3(dipn)]BF4 (1), [Re(CO)3(N′Medipn)]PF6 (2), [Re(CO)3(N,N-Me2dipn)]BF4 (3), [Re(CO)3(trenH)](PF6)2 (4), [Re(CO)3(trpnH)](PF6)2 (5), [Re(CO)3(aepn)]PF6 (6), and [Re(CO)3(tacn)]PF6 (7)

Table 2.4.

Selected 1H NMR Chemical Shifts (ppm) of [Re(CO)3(dipn)]BF4 (1), [Re(CO)3(N′Medipn)]PF6 (2), [Re(CO)3(N,N-Me2dipn)]BF4 (3), [Re(CO)3(trenH)](PF6)2 (4), [Re(CO)3(trpnH)](PF6)2 (5), [Re(CO)3(aepn)]PF6 (6), and [Re(CO)3(tacn)]PF6 (7) at 25 °C......23 Table 3.1. Crystal Data and Structure Refinement for [Re(CO)3(DAE)]BF4 (1), [Re (CO)3(MAE)]PF6 (2), [Re(CO)3(MAEH)F]PF6 (3), and [Re(CO)3(EAE)]BF4 (4)

Table 3.2.

Selected Bond Distances (Å) and Angles (deg) for [Re(CO)3(DAE)]BF4 (1),a [Re(CO)3(MAE)]PF6 (2), [Re(CO)3(MAEH)F]PF6 (3), and [Re(CO)3(EAE)]BF4 (4)..................50 Table 3.3.

1H NMR Chemical Shifts (ppm) of [Re(CO)3(DAE)]BF4 (1), [Re(CO)3(MAE)]PF6 (2), and [Re(CO)3(EAE)]BF4 (4) in DMSO-d6 at 25 °C and Selected NH Shifts in Acetonitrile-d355 Crystal Data and Structural Refinement for [Re(CO)3(5,5′Table 4.1.

Me2bipy)(HNC(CH3)NHR)]BF4 Complexes

Table 4.2.

Selected Bond Distances (Å) and Angles (deg) for [Re(CO)3(5,5′Me2bipy)(HNC(CH3)NHR)]BF4 Complexes

Table 4.3.

Selected 1H NMR Shifts (ppm) for Re(CO)3[(5,5′-Me2bipy)(HNC(CH3)NHR)]BF4 in Acetonitrile-d3 at 25 °C

Table 4.4.

Distribution (%) of E′ and Z Isomers of [Re(CO)3(5,5′-Me2bipy) (HNC(CH3)NHR)]BF4 in Acetonitrile-d3 at 25 °C

Table 5.1.

Crystal Data and Structure Refinement for [Re(CO)3(CH3CN)3]PF6 and [Re(CO)3(L) (HNC(CH3)OCH3)]BF4 (L = bipy, 4,4′-Me2bipy, 5,5′-Me2bipy, and 6,6′-Me2bipy)

Table 5.2.

Selected Bond Distances (Å) and Angles (deg) for [Re(CO)3L(HNC(CH3)OCH3)]BF4 (L = Bidentate Ligand)

Table 5.3.

Ligand Deformation in Octahedral Rhenium Complexes

vii Table 6.1.

Crystal Data and Structure Refinement for [Re(CO)3(N(SO2Me)dpa)]PF6 (1) and [Re(CO)3(N(SO2tmb)dpa)]PF6 (2)

Table 6.2.

Selected Bond Distances (Å) and Angles (deg) for [Re(CO)3(N(SO2Me)dpa)]PF6 (1), and [Re(CO)3(N(SO2tmb)dpa)]PF6 (2)

Table 6.3.

Selected 1H NMR Shifts (ppm) in DMSO-d6 for dpaSO2Me, [Re(CO)3(N(SO2Me)dpa)]PF6 (1), Pt(N(SO2Me)dpa)Cl2, dpaSO2tmb, [Re(CO)3(N(SO2tmb)dpa)]PF6 (2), and Pt(N(SO2tmb)dpa)Cl2

Table 6.4.

Selected 1H NMR Shifts (ppm) in DMSO-d6 for T(N(SO2C6H4)dpa)P and [{Re(CO)3}4T(N(SO2C6H4)dpa)P](BF4)4 (4)

–  –  –

Figure 2.1.

Designation of endo and exo protons in 5-membered (left) and 6-membered (right) rings, as illustrated based on the molecular structure of [Re(CO)3(aepn)]PF6. The exo-NH or exoCH protons point away from the carbonyl ligands and the endo-NH or endo-CH protons point toward the carbonyl ligands.

Figure 2.2.

ORTEP plots of the cations of [Re(CO)3(dipn)]BF4 (1), [Re(CO)3(N′-Medipn)]PF6 (2), [Re(CO)3(N,N-Me2dipn)]BF4 (3), and [Re(CO)3(aepn)]PF6 (6). Thermal ellipsoids are drawn with 50% probability. Only one of the independent molecules is shown for 1 (Z′ = 3) and for 3 (Z′ = 2).

Figure 2.3.

ORTEP plots of the cations of [Re(CO)3(trenH)](PF6)2 (4) and [Re(CO)3 (trpnH)](PF6)2 (5). Thermal ellipsoids are drawn with 50% probability.

Figure 2.4.

ORTEP plot of the cation of [Re(CO)3(tacn)]PF6 (7). Thermal ellipsoids are drawn with 50% probability

Figure 2.5.

Designations of the exo-C and endo-C conformations for 5- and 6-membered rings of fac-[Re(CO)3L]n complexes. Re is directed away from the viewer and the nitrogens are blue. The terminal N of the ring of interest is on the right, the central N is on the left, and the terminal N (but not the chain methylene groups) of the other ring is in the axial position. Note that for 5membered rings, the chirality of the ring pucker is also designated.

Figure 2.6.

1H NMR spectra of [Re(CO)3(dipn)]PF6 (1), [Re(CO)3(aepn)]PF6 (6), and [Re(CO)3(dien)]PF6 (top) in DMSO-d6 at 25 °C (* water peak). Full spectra for 1 and 6 are presented in Figure A.1 in Supporting Information.

Figure 2.7.

Effect of Cl– on ∆δ of the NH signals of [Re(CO)3(dipn)]PF6 (1) and [Re(CO)3(tacn)]PF6 (7) (designated as tacn-NH) in DMSO-d6 at 25 °C

Figure 2.8.

Effect of Cl– on ∆δ of the NH signals of [Re(CO)3(N′-Medipn)]PF6 (2) in DMSO-d6 at 25 °C.

Figure 2.9.

Effect of Cl– on ∆δ of the NH signals of [Re(CO)3(aepn)]PF6 (6) in DMSO-d6 at 25 °C. A COSY spectrum was used to assign the NH signals

Figure 2.10.

Effect of Cl–, Br–, and I– on ∆δ of the exo-NH signals of [Re(CO)3(dipn)]PF6 (1) in acetonitrile-d3 at 25 °C

Figure 2.11.

Effect of [ReBr6]2- on ∆δ of the ND signals of [Re(CO)3(dipn-d5)]PF6 in DMSO-d6 at 25 °C.

Figure 3.1.

ORTEP plot of the cation in [Re(CO)3(DAE)]BF4. Thermal ellipsoids are drawn with 50% probability

ix Figure 3.2.

ORTEP plots of the cations in (a) [Re(CO)3(MAE)]PF6, (b) [Re(CO)3(MAEH)F]PF6, and (c) [Re(CO)3(EAE)]BF4. Thermal ellipsoids are drawn with 50% probability.

Figure 3.3.

Designation of the exo-NH proton (pointing away from the carbonyl groups and toward the hydrophobic pocket of the ligand) of [Re(CO)3(MAE)]PF6 and [Re(CO)3(EAE)]BF4.

N4H is not classified as either endo or exo

Figure 3.4.

1H NMR spectrum showing NH signals of [Re(CO)3(DAE)]BF4 in DMSO-d6 at 25 °C (top), in acetonitrile-d3 at 25 °C (middle), and in acetonitrile-d3 at -5 °C (bottom).................57 Figure 3.5.

Designation of the N4Ha and N4Hb protons of [Re(CO)3(DAE)]BF4, indicating the proximity of N4Hb to the methyl group

Figure 3.6.

Change in chemical shift (∆δ, ppm) of the NH signals of [Re(CO)3(MAE)]PF6 (5 mM) caused by added Cl– in DMSO-d6 at 25 °C.

Figure 3.7.

Change in chemical shift (∆δ, ppm) of the NH signals of [Re(CO)3(MAE)]PF6 (5 mM) caused by added Cl– in acetonitrile-d3 at 25 °C

Figure 3.8.

Change in chemical shift (∆δ, ppm) of the NH signals of [Re(CO)3(DAE)]BF4 (5 mM) caused by added Cl– in acetonitrile-d3 at 25 °C

Figure 3.9.

1H NMR spectra of [Re(CO)3(MAE)]PF6 (5 mM) in DMSO-d6 at 25 °C before (top) and 20 min after (bottom) addition of OH– (1.7 mM). The multiplet at ~4.2 ppm arises from one of the C7H2 protons.

Figure 4.1.

Conceivable fac-[Re(CO)3(L)(HNC(CH3)NHR)]+ isomers, in which L is a bidentate ligand denoted by N–N donor atoms.

Figure 4.2.

[Re(CO)3(L)(HNC(CH3)NHR)]+ isomers observed upon treatment of [Re(CO)3(5,5′Me2bipy)(CH3CN)]+ with RNH2 in acetonitrile at 25 °C.

Figure 4.3.

ORTEP plots of the cations in [Re(CO)3(5,5′-Me2bipy)(E′-HNC(CH3) NHCH(CH3)2)]BF4 (2), [Re(CO)3(5,5′-Me2bipy)(E′-HNC(CH3)NHCH2CH(CH3)2)]BF4 (3), [Re(CO)3(5,5′-Me2bipy)(E′-HNC(CH3)NHC(CH3)3)]BF4 (4), and [Re(CO)3(5,5′-Me2bipy)(E′HNC(CH3)NHCH2C6H5)]BF4 (5). Thermal ellipsoids are drawn with 50% probability..............78 Figure 4.4.

ORTEP plot of the cation in [Re(CO)3(5,5′-Me2bipy)(Z-HNC(CH3)NH2)]BF4 (7).



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