Describes the preparation and characterisation of a novel series of organoplatinum(II) complexes with hydrogen-bonding functionality.Thesis (M.Sc.)--University of Adelaide, Dept. of Chemistry, 200

Crisp, Michael G.

Adelaide Research &amp; Scholarship

O r g a n o p l a t i n u m ( l l )  G o m p l e x e s  w i t hH y d  r o g e n - B o n d  i  n g  F  u  n c t i o n a l  i t Ya n d  T h e i r  P o t e n t i a l  U s e  a sM o l e c u l a r  R e c e p t o r s  f o r  A d e n in eA  T h e s i s  S u b m i t t e d  f o r  t h eD e g r e e  o f  M a s t e r  o f  S c i e n c eM i c h a e l  G .  C r i s p  B . S c  ( H o n s . )A D E L A I D EU N I V E R S I T YA U S T R A L I AD e p a r t m e n t  o f  C h e m i s t r yJ a n u a r y  2 0 0 2Y Oc B u c EErrataTable of contents (pages viii and ix): The titles of complexes should commence with"trans" îot"Trans"" not "ComPlexations PlaY,." not "...host binding' ""Page 10, paragraph 1: Should read "Complexation plays ' 'Page 1 l,patagraph 1: Should read"" 'binding to the hostPage20:Theiodoligandisused.inthis'reactionas(36)ismorereactivethanthecorresponding chlorã complex (35) in the presence of silvel ions'Page23,Table 1: "na" and"nla" refer to the term "not applicable"',Iine 2:Picolinic acid complexes (50). - (53) contained moreLnt p.oton, than the other isomers owing to their low symmetry'complicated rH NMR spectra'Page2g,paragraph2,Iine_2:Shouldstart..Complexes(52)and(53)weretheonlytwocomplexes.. '"page 34:Entry for (54) H3 should read "Obscu'ed by PMePh"' and not "Obscure d byPMePhr"' Entry ror (5i) Hs should read "As for H4" not "e"'Page39:Preparationoftheplatinum(Il)-iodocomplex(59)isshowninScheme2.6.Page 4|,Table 9 and Page 52,Tab1e 1 1: The IR spectra were recofded as Nujol mulls.Page 60, paragraph 2: Should read "r4N" not "Nr14"PageT2,paragraph 1, line -3: shotrld be "possess" not "posses"'Page73:2D NMR spectra were t'ecorded at 600 MHz and not 300 MHz'I1 llIl, lIIIlD e c l a r a t i o nT h i s  t h e s i s  c o n t a i n s  n o  m a t e r i a l  w h i c h  h a s  b e e n  a c c e p t e d  f o r  t h e  a w a r d  o f  a n y  o t h e r  d e g r e e  o rd i p l o m a  i n  a n y  u n i v e r s i t y  a n d ,  t o  t h e  b e s t  o f  m y  k n o w l e d g e ,  c o n t a i n s  n o  m a t e r i a l  p r e v i o u s l yp u b l i s h e d  o r  w r i t t e n  b y  a n o t h e r  p e r s o n ,  e x c e p t  w h e r e  d u e  r e f e r e n c e  i s  m a d e .I  c o n s e n t  f o r  t h e  t h e s i s  b e i n g  m a d e  a v a i l a b l e  f o r  p h o t o c o p y i n g  a n d  l o a n  i f  a c c e p t e d  f o r  t h e  a w a r do f  t h i s  d e g r e e .M i c h a e l  G .  C r i s pJ a m a r y  2 0 0 2l lA c k n o w l e d g e m e n t sD r .  L o u i s  M .  R e n d i n a  p r o v i d e d  m e  w i t h  t h e  o p p o r t u n i t y  t o  d o  t h i s  p r o j e c t .  I  w o u l d  l i k e  t o  t h a n kh i m  f o r  p r o v i d i n g  m e  w i t h  t h i s  o p p o r t u n i t y ,  a n d  f o r  a l l o w i n g  m e  t o  d e v e l o p  m y  o \ ü n  p r o j e c t  a n dh e l p i n g  m e  t u r n  m y  i d e a s  f o r  t h i s  p r o j e c t  i n t o  r e a l i t y .T h a n l c y o u  t o  D r .  E d w a r d  T i e k i n k  f o r  h i s  i n v a l u a b l e  a s s i s t a n c e  w i t h  t h e  c r y s t a l l o g r a p h i c  d a t a .T h a n k s  t o  m y  f e l l o w  l a b o r a t o r y  l 0  m e m b e r s  f o r  t h e i r  s u p p o r t ,  e n c o u r a g e m e n t  a n d  f r i e n d s h i po v e r  t h e  c o u r s e  o f  t h i s  p r o j e c t ,  S u s a n  W o o d h o u s e ,  D a v i d  G a l l a s c h ,  D a v i d  C l a r k e ,  J e a n  T o d d ,D o u g  S m y t h ,  B e n  E l l i s ,  a n d  D a n i e l a C a t a z z a .I  w o u l d  l i k e  t o  t h a n k  S a r a h  w h o  m a r r i e d  m e  o n  t h e  3 0 t h  o f  S e p t e m b e r  2 0 0 1 .  T h a n þ o u  S a r a t r  f o rb e i n g  s o  s u p p o r t i v e  d u r i n g  t h e  c o w s e  o f  m y  w o r k .  Y o u  p r o v i d e d  m e  w i t h  a  g r e a t  m o t i v a t i o n  t of i n i s h  t h i s  p r o j e c t  a n d  a l w a y s  e n c o u r a g e  m e  t o  f o l l o w  m y  d r e a m s .I  w o u l d  l i k e  t o  t h a n k  m y  M u m  a n d  m y  D a d  f o r  t h e i r  c o n t i n u e d  s u p p o r t  i n  e v e r y t h i n g  t h a t  I  d o .  Iw o u l d  l i k e  t o  t h a n k  t h e m  f o r  l i s t e n i n g  t o  m y  c o n t i n u a l  r a n t i n g  a b o u t  t h e  u p s  a n d  d o w n s  o f  m yp r o j e c t .i i iA b s t r a c tT h e  p r e p a r a t i o n  a n d  c h a r a c t e r i s a t i o n  o f  a  n o v e l  s e r i e s  o f  o r g a n o p l a t i n u m ( I l )  c o m p l e x e s  w i t hh y d r o g e n - b o n d i n g  f u n c t i o n a l i t y  a r e  d e s c r i b e d .  T h e  m o n o n u c l e a r  p l a t i n u m ( I l )  c o m p l e x e s  o f  t h et y p e  t r a n s - [ P t ( o - a r y l ) L ( P P h 3 ) 2 ] O T f  ( L  :  n i c o t i n i c  a c i d ,  p i c o l i n i c  a c i d ,  i s o n i c o t i n i c  a c i d )  a n d  t h ed i n u c l e a r  c o m p l e x e s  o f  t h e  t y p e  t r a n s - [ P t ( o - a r y l ) ( P P h 3 ) ( p - Y ) P t ( o - a r y l ) ( P P h 3 ) 2 ] ( O T Ð z  ( Y  :  4 , 4 ' -b i p y r i d y l ,  4 , 7  - p h e n a n t h r o l i n e ,  4 , 4 '  - d i p y r a z o l y l m e t h a n  e ,  l , l ' - p h e n y l - 4  , 4 ' - d i p y r a z o l y l m e t h a n e )w e r e  i n v e s t i g a t e d .  T h e  c o m p l e x e s  w e r e  p r i m a r i l y  c h a r a c t e r i s e d  b y  m u l t i n u c l e a r  1 3 r P ,  t H ¡  t - O  a n d2 - D  N M R  s p e c t r o s c o p y ,  I R  s p e c t r o s c o p y  a n d ,  i n  s o m e  c a s e s ,  X - r a y  c r y s t a l l o g r a p h y .  T h e s ep l a t i n u m ( I )  c o m p l e x e s ,  b o t h  m o n o - n u c l e a r  a n d  d i - n u c l e a r ,  h a v e  t h e  p o t e n t i a l  t o  a c t  a s  h o s t s  f o rn u c l e o b a s e  g u e s t s  s u c h  a s  a d e n i n e ,  a n d  t h i s  w a s  i n v e s t i g a t e d  a l s o .  T h e  m o n o - p l a t i n u m  c o m p l e x e sw e r e  f o u n d  t o  i n t e r a c t  w i t h  t h e  g u e s t  9 - s e c - p e n t y l a d e n i n e  i n  a  v a r i e t y  o f  w a y s  i n  C D C b  s o l u t i o ni n c l u d i n g ,  l : 1 ,  2 ; l  a n d  i n  s o m e  c a s e s  3 :  I  a s s o c i a t i o n  r a t i o s  a t  b o t h  t h e  V / a t s o n - C r i c k  a n d  t h eH o o g s t e e n  s i t e .  T h e  d i n u c l e a r  p l a t i n u m ( I l )  m o l e c u l a r  " t w e e z e r s "  w e r e  f o u n d  t o  b i n ds i m u l t a n e o u s l y  t o  t w o  9 - s e c - p e n t y l a d e n i n e  m o l e c u l e s  i n  C D C I 3  s o l u t i o n .l vA b b r e v i a t i o n sG e n e r a l :od e g r e e sd e g r e e s  C e l s i u sc h a n g e  i n  f r e e  e n e r g yo n e  d i m e n s i o n a lt w o  d i m e n s i o n a lA n g s t r o mc e n t i m e t r ed e o x y r i b o n u c l e i c  a c i d4 , 4 '  -  d i p y  r  a z o l y l m e t h a n eg r a mh o u ¡K e l v i nm a s s  s p e c t o m e û ym i l l i l i t r eC F ¡  S O E ' ,  t r i f l u o r o m e t h a n e s u l f o n a t ep h e n y lt e t r a t r y d r o f u r a nO CA G1 - D2 - DÅc mD N AD P Z MûbhKM Sm LO T f ,  t r i f l a t eP hT H FN u c l e a r  m a g n e t i c  r e s o n a n c e  s p e c t r o s c o p y :ô  n u c l e a r  m a g n e t i c  r e s o n a n c e  c h e m i c a l  s h i f t  i n  p p mt H  N M R  p r o t o n  n u c l e a r  m a g n e t i c  r e s o n a n c et t P { t H }  N M R  p r o t o n  d e c o u p l e d  3 r P  n u c l e a r  m a g n e t i c  r e s o n a n c ed  d o u b l e td d  d o u b l e t  o f  d o u b l e t sH z  H e r t zI  n u c l e a r  s p i n  q u a n t u m  n u m b e rm  m u l t i p l e tvI l v 4 H z" J r iN M Rp p mStm e g a h e r t zn  b o n d  c o u p l i n g  c o n s t a n t  b e t w e e n  n u c l e i  i  a n d  jn u c l e a ¡  m a g n e t i c  r e s o n a n c ep a r t s  p e r  m i l l i o ns i n g l e tt r i p l e tv tT a b l e  o f  C o n t e n t sD e c l a r a t i o nA c k n o w l e d g e m e n t sA b s t r a c tA b b r e v i a t i o n sT a b l e  o f  C o n t e n t sC h a p t e r  I  I n t r o d u c t i o nl . l  S e l f  A s s e m b l yI  . 2  D N A / R N A  N u c l e o b a s e sI  . 3  P l a t i n u m  C o m p l e x e s  w i t h  H y d r o g e n - B o n d i n g  F u n c t i o n a l i t yI  . 4  M o l e c u l a r  T w e e z e r s  C o n t a i n i n g  P l a t i n u m ( I  I )2 . 1  S y n t h e s i s  a n d  C h a r a c t e r i s a t i o n  o f  l o d o p l a t i n u m ( I l )  P r e c u r s o r  C o m p l e x e s2 . 2  S y n t h e s i s  a n d  C h a r a c t e r i s a t i o n  o f  M o n o n u c l e a rP l a t i n u m ( I l )  C o m p l e x e s  w i t h  H y d r o g e n - B o n d i n g  F u n c t i o n a l i t y2 . 3  p K a D e t e r m i n a t i o n s  f o r  C o m p l e x e s  ( 4 3 ) ,  ( 4 6 ) ,  ( 4 7 ) ,  ( 4 8 ) ,  a n d  ( 5 1 )ii il l li vv i iIC h a p t e r  2  P r e p a r a t i o n  a n d  C h a r a c t e r i z a t i o n  o f  M o n o n u c l e a rP l a t i n u m ( I l )  C o m p l e x e s  w i t h  H y d r o g e n - B o n d i n g  F u n c t i o n a l i t y  1 9Il 0t 41 6t 92 74 4C h a p t e r  3  P r e p a r a t i o n  a n d  C h a r a c t e r i s a t i o n  o f  D i n u c l e a rO r g a n o p l a t i n u m ( I l )  C o m p l e x e s  w i t h  H y d r o g e n - B o n d i n g  F u n c t i o n a l i t y  4 7C h a p t e r  4  M o l e c u l a r  R e c o g n i t i o n  o f  A d e n i n e  b yP l a t i n u m ( I l )  C o m p l e x e s  w i t h  H y d r o g e n - B o n d i n g  F u n c t i o n a l i t y  5 64 .  1  A s s o c i a t i o n  S t u d i e s  o f  M o n o n u c l e a rP l a t i n u m ( I )  C o m p l e x e s  w i t h  9 - s e c - p e n t y l a d e n i n e4 . 2  A s s o c i a t i o n  S t u d i e s  o f  D i n u c l e a r6 5v l lP l a t i n u m ( I l )  C o m p l e x e s  ( 6 7 )  a n d  ( 6 8 )  w i t h  9 - s e c - p e n t y l a d e n r n eC h a p t e r  5  C o n c l u s i o nC h a p t e r  6  E x p e r i m e n t a lt r a n s - i o d o p h e n y l - b i s ( t r i p h e n y l p h o s p h i n e ) p l a t i n u m ( I I )  ( 3  7 )t r a n s - i o d o - b i s ( m e t þ l d i p h e n y l p h o s p h i n e ) p h e n y l p l a t i n u m ( I l )  ( 3 8 )t r a n s - i o d o p h e n y l b i s ( t r i e t h y l p h o s p h i n e ) p l a t i n u m ( I l )  ( 3 9 )t r a n s - i o d o p h e n y l - b i s ( t r i c y c l o h e x y l p h o  s p h i n e ) p l a t i n u m ( I l )  ( 4 0 )T r  a n  s  -  ( n r c o t i n i c  a c i d ) p h e n y lb i s ( t r i p h e n y l p h o s p h i n e ) p l a t i n u m ( I l )  t r i f l  a t e  ( 4 2 )T r  a n  s  -  ( i s o n i c o t i n i c  a c i d ) p h e n y lb i s ( m e t h y l d i p h e n y l p h o s p h i n e ) p l a t i n u m ( I l )  t n f l a t e  ( 4 7 )T r  a n  s  -  ( i s o n i c o t i n i c  a c  i d ) p h e n y lb i s ( t r i e t þ l p h o s p h i n e ) p l a t i n u m ( I l )  t r i f l  a t e  ( 4 8 )7 T7 47 57 67 67 67 67 7T r  a n  s  -  ( r i c o t i n i c  a c i  d ) p h e n y  Ib i s ( m e t h y l d i p h e n y l p h o s p h i n e ) p l a t i n u m ( I l )  t r i f l a t e  ( 4 3 )T r a n s - ( n r c o t i n i c  a c i d ) p h e n y l b i s ( t r i e t þ l p h o s p h i n e ) p l a t i n u m ( I l )  t r i f l a t e  ( 4 4 )  7 7T r  a n  s  -  ( r u c o t i n i c  a c i d ) p h e n y lb i s ( t r i c y c l o h e x y l p h o s p h i n e ) p l a t i n u m ( I l )  t r i f l  a t e  ( 4 5 )7 8T r  a n  s  -  ( i s o n t c o t i n i  c  a c i d ) p h e n y lb i s ( t r i p h e n y l p h o s p h i n e ) p l a t i n u m ( I l )  t r i f l  a t e  ( 4 6 ) 7 87 77 87 9v l l lT r  a n s  -  ( i s o n i c o t i n i c  a c i d ) p h e n y lb i s ( t r i c y c l o h e x y l p h o s p h i n e ) p l a t i n u m ( I l )  t r i f l  a t e  ( 4 9 )T r  a n  s  -  ( ç i c o l i n i c  a c i d ) P h e n Y lb i s ( t r i p h e n y l p h o s p h i n e ) p l a t i n u m ( I l )  t r i f l  a t e  ( 5 0 )T r  a n  s  - ( p i c o t i n i c  a c i d ) P h e n Y lb i s ( m e t h y l d i p h e n y l p h o s p h i n e ) p l a t i n u m ( I l )  t r i f l  a t e  ( 5  1 )T r  a n  s  -  ( p i c  o l i n i c  a c i d ) P h e n Y lb i s ( t r i e t h y l p h o s p h i n e ) p l a t i n u m ( I l )  t r i f l  a t e  ( 5 2 )T r  a n  s  - ( p i c  o l  i n i c  a c i  d ) P h e n Y lb i s ( t r i c y c l o h e x y l p h o s p h i n e ) p l a t i n u m ( I l )  t r i f l a t e  ( 5 3 )7 9T r  a n  s  -  ( r u c o t i n a m i d e ) P h e n Y lb i s ( m e t þ l d i p h e n y l p h o s p h i n e ) p l a t i n u m ( I l )  t r i f l  a t e  ( 5 5 )T r a n s - i o d o Q . { - m e t þ l b e n z a m i d e ) b i s ( t r i p h e n y l p h o s p h i n e ) p l a t i n u m ( I l )  ( 5 9 )  8 1T r a n s - ( i s o n r c o t i n a m i d e ) p h e n y lb i s ( m e t h y l d i p h e n y l p h o s p h i n e ) p l a t i n u m ( I l )  t r i f l  a t e  ( 5 4 )T r  a n s  - ¡ t - 4 , 4 '  - b i p y r i d i n e b i s  [ ( N - m e t þ l b e n z a m i d e )b i s ( t r i p h e n y l p h o s p h i n e ) p l a t i n u m ( I l ) l  b i s ( t r i f l  a t e )  ( 6 5 )T r  a n s  - ¡ t - 4 , 7 - p h e n a n t h r o l i n e b i  s  f N - m e t þ l b e n z a m i d e ]b i s ( t r i p h e n y l p h o s p h i n e ) p t a t i n u m ( I l ) l  b i s ( t r i f l a t e )  ( 6 6 )T r  a n s  - ¡ t - 4 , 4 '  - d i p y r a z o l y l m e t h a n e b i s  [ ( N - m e t þ l b e n z a m i d e )b i s ( t r i p h e n y l p h o s p h i n e ) p l a t i n u m ( I l ) l  b i s ( t r i f l a t e )  ( 6 7 )8 07 97 98 08 08 18 28 28 1T r  a n s  - ¡ t - 1 , 1 '  - p h e n y l - 4 , 4 '  - d i p y r a z o l y l m e t h a n e b i s  [ ( N - m e t þ l b e n z a m i d e )l xb i s ( t r i p h e n y l p h o s p h i n e ) p l a t i n u m ( I l ) l  b i s ( t r i f l  a t e )  ( 6 8 )P r e p a r a t i o n  o f  S a m p l e s  f o r  J o b  P l o t sD e t e r m i n a t i o n  o f  p K a  v a l u e sR e f e r e n c e s8 28 38 48 5x

Organoplatinum(II) complexes with hydrogen-bonding functionality and their potential use as molecular receptors for adenine

https://digital.library.adelaide.edu.au/dspace/bitstream/2440/109743/2/01front.pdf

Organoplatinum(II) complexes with hydrogen-bonding functionality and their potential use as molecular receptors for adenine

Abstract

Similar works

Full text

Available Versions

Adelaide Research & Scholarship

Organoplatinum(II) complexes with hydrogen-bonding functionality and their potential use as molecular receptors for adenine

Abstract

Similar works

Full text

Available Versions

Adelaide Research &amp; Scholarship

Adelaide Research & Scholarship