Bimetallic nano alloy architecture on a special polymer: Ni or Cu merged with Pd for the promotion of the Mizoroki–Heck reaction and the Suzuki–Miyaura coupling

Article abstract of DOI:10.1007/s12039-020-01870-6

Abstract: Novel Ni-Pd and Cu-Pd bimetallic nano alloys was designed and heterogenized on the highly robust ABPBI [poly(2,5-benzimidazole)] polymer in high yields using NaBH₄ as reducing agent. These were versatile ligand free catalysts for the Mizoroki–Heck reaction and Suzuki–Miyaura coupling. The bimetallic Ni-Pd-ABPBI catalyst for the Mizoroki–Heck reaction of 4-iodo anisole could be recycled 5 times with high yields. Aryl bromides could also be activated for the Mizoroki–Heck reaction using Cu-Pd-ABPBI NP catalysts, with moderate yields. Graphic abstract: Synopsis Novel bimetallic Ni-Pd and Cu-Pd nano alloys, heterogenized on the robust ABPBI [poly(2,5-benzimidazole)] polymer using NaBH₄ as reducing agent, is described. These were versatile ligand free, noble metal conservative catalysts, for the Mizoroki–Heck reaction and the Suzuki–Miyaura coupling. Aryl bromides were activated for the Mizoroki–Heck reaction using the Cu-Pd-ABPBI catalyst.[Figure not available: see fulltext.]

Full text of DOI:10.1007/s12039-020-01870-6

J. Chem. Sci. ( 2 0 2 1 ) 1 3 3 : 8
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REGULAR ARTICLE
Bimetallic nano alloy architecture on a special polymer: Ni or Cu
merged with Pd for the promotion of the Mizoroki–Heck reaction
and the Suzuki–Miyaura coupling
a , b
V I J A Y P P A T IL , A B H I J I T A K A S H I D , B H A N U PR A T A P S S O L A N K I ,
a
b , d
c , d
U L HA S K K H A R U L a n d S U R E S H I Y E R
a ,d ,
*
a
O r g a n i c C h e m i s t ry D i v i s i o n , N a t i o n a l C h e m i c a l L a b o r a t o r y , D r . H o mi B h a b h a R o a d ,
P a s h a n , P u n e 4 1 1 0 0 8 , M a h a r a s h t ra , I n d i a
b
C h em i c a l E n g i n e e r i n g a n d P ro c e s s D e v e l o p m e n t, N a t i o n a l C h e m i c a l L a b o r a t o r y ,
P a s h a n , P u n e 4 1 1 0 0 8 , M a h a r a s h t ra , I n d i a
c
P o l y m e r S c i e n c e a n d E n g i n e e r i n g D iv is i o n , N a t i o n a l C h e m i c a l L a b o r a t o r y , D r . H o mi B h a b h a R o a d ,
P a s h a n , P u n e 4 1 1 0 0 8 , M a h a r a s h t ra , I n d i a
d
A c ad e m y o f S c i e n t i fi c a n d I n n o v a t i v e R e s e a r c h ( A c S I R ) , N e w D e l h i 1 1 0 0 2 5 , I n d ia
E - m a i l : s . i y e r @n c l . re s. i n
M S r e c e i v e d 2 8 A u gu s t 2 02 0 ; r e v i s e d 2 3 O c t o b e r 2 0 2 0; a c c e p t e d 2 9 O c t o b e r 2 0 2 0
Abstract. N o v e l N i - Pd a n d C u - Pd b i m e t a l l ic n a n o a l l o y s w a s d e s i g n e d a n d h e t e r o g e n i z e d o n t h e h ig h l y
r o b u s t A B P B I [ p o l y ( 2 , 5 - b e n z i m i d a z o l e ) ] p o l y m e r i n h i g h y i e l d s u s i n g N a B H a s r e d u c i n g a g e n t. T h e s e w e re
4
v e r s at i l e l i g a n d f re e c a t a l y s t s f o r t h e M i z o r o k i – H e c k r e a c t io n a n d S u z u k i – M i y a u r a c o u p l in g . T h e b i m e t a ll i c
N i - P d - A B P B I c a t a l y s t f o r t h e M i z o ro k i – H e c k r e a c ti o n o f 4 - i o d o a n i s o l e c o u ld b e r e c y c l e d 5 t im e s w it h h ig h
y i el d s . A ry l b r o mi d e s c o u l d a l s o b e a c t i v a t e d f o r t h e M i z o r o k i – H e c k r e a c t io n u s i n g C u - P d - A B P B I N P
c at al y s t s , w i t h m o d e r a t e y i e l d s .
Keywords. B i m e t a l l i c n a n o a l l o y s ; M i z o r o k i – H e c k r e a c ti o n ; S u z u k i c o u p l in g ; N i - P d - A B P B I ; C u - P d -
A B P B I .
1. Introduction
i n ex p e n s i v e t r a n s i t i o n m et al s a n d / o r r ec o v e r y a n d
r e cy cl ab i l i t y o f t h e c at al y t i c s y s t e m w i t h i m p r o v e d
s e l e c t i v i t y a n d c at a l y t i c e ffi c i e n c y . B i m et al l i c c a t a -
l y s t s a r e k n o w n t o b e s u p er i o r t o t h e c o r r es p o n d i n g
m o n o m et al l i c c at a l y s t s f o r v a r i o u s r ea c t i o n s .
T h e s y n er g i s t i c e ff e c t o f b i me t a l l i c c at a l y s i s h a s
b e e n d e s c r i b e d i n t h e i s o l a t e d m et al a t o m g e o m e t r y
8
s t ra t e g i es f o r c at a l y s i s o f h y d ro g e n a t i o n r e ac t i o n . I n
N a n o p a r t i c l e s a r e s t a te -o f- t he - a r t f or c a t a l ys i s w h i l e
b i m e t a l l i c n a n o a l lo ys e x h i b it g r e a t e r e n ha nc e m e n t i n
e f fi c i e n c y d u e t o t he h a rm o n ic i nt e r a c ti o n o f a n o b l e
m e t a l w i t h a l i g h t e r m e ta l , t hu s b e c o m i n g a s u c -
c es s f u l & fl o u r i s h i n g s t r a t e g y f o r n o b l e m e ta l c at a l -
y s i s . H e t e r o ge n i z a t i on o f n o b le m e ta l c a t a l y s t s o n
i n s o l u b l e s u p p o r t s l ik e S i O , A l O , i s a c o m m o n a n d
s u c c es sf ul s o l u t i o n b e i ng e x p e r im e nt e d . R e c o v e r y o f
n o b l e m et a l a n d e f fi c i e n t u s e i n s m a l l e r q u a n t i t i e s
m a k e s t h i s a n i n d us tr ia ll y v i a bl e a l t e r n a ti v e a n d n e x t
g e n e r a t i o n c a t a l ys is .
C - C b o n d f o r m i ng r e a c t io n s p la y s a p i v o t a l r o l e i n
m i m i c k i n g t h e n a t u r e i n t he l a b or a t or i e s a n d t o
d e v e l o p m o l e c u l a r s c a f fo l d s a n d o r g a n i c c o m p o u n d s
p o s s e s si n g c o mp l e x m o l e c u l a r a r c h i te c t u r e . T h e
p r a c t i c al s o l u t i o n l ie s i n t he d e v e lo p me n t o f
1– 7
2
2 3
b i me t a l l i c c at a l y s i s , t h e e x p l o i t at i o n o f m o r e e x p e n -
s i v e n o b l e m et al i s c o n s e r v e d , w i t h t h e c at a l y s i s b e i n g
a u g m e n t e d b y a l e s s e x p e n s i v e c o - c at al y s t . I n e x p e n -
s i v e N i c o m p l e x e s , C u s a l t s a n d h e t e r o g e n e o u s c a t a -
l y s t b a s e d o n N i , C u , C o a n d M n h a v e a ct i v a t e d t h e
M i z o r o k i – H ec k r ea c t i o n a n d S u z u k i – M i y a u r a
9– 1 4
c o u p l i n g .
L i g a n d f r ee P d ( O A c ) a ct i v a t e s a r y l b r o m i d e s f o r
2
1 5
t h e M i z o r o k i – H ec k r e ac t i o n . B o z el l a n d V o g t h a v e
* F o r c o r re s p o n d e n c e
Electronic supplementary material: The online version of this article (https://doi.org/10.1007/s12039-020-01870-6) contains
supplementary material, which is available to authorized users.

8
P a g e 2 o f 1 2
J. Chem. Sci. ( 2 0 2 1 ) 1 3 3 :8
d e s c r i b e d t h e c o - o p e r a ti ve e f f e c t o f N i B r w i t h 2. Experimental
2
P d ( O A c ) i n t h e p re s e n c e o f e x c e s s N a I t o a c t iv a t e t h e
2
2 . 1 General procedure for the Ni-Pd-ABPBI
catalyzed Mizoroki–Heck reaction of aryl iodides
and bromides
r e l a t i v e l y u n r e a c t i v e a r y l c h l o r id e s f or t he M i z o r o k i –
1 6
H e c k r e a c t i o n. T h e P d -P M I [ p o ly (i m i d az o l e / P a l l a -
d i u m ) ] a s a s e l f -a s s e m b l in g s u pp o r t e d c a t a l y s t h a s
1 7
b e e n e x e m pl i fi ed f o r a l l yl a ti on a n d S u z u k i c o u p l i n g .
T o a s o l u t i o n o f N i - P d - A BP B I ( 0 . 0 5 0 g , 0 . 1 7 8 m m o l )
i n 5 m l s o l v e n t ( PE G -4 0 0 ) w a s a d d e d a ry l i o d i d e
( 1 m mo l ) , a l k e n e ( 1 . 5 m mo l ) a n d b a s e , C y N Me
H e t e r og en i za t i o n o f b i m e t a l li c c a t a l ys ts o n p o l y m er
s u p p o r t h a s t h e a d v a n t a g e s o f c a t a l ys t r e c o v e r y a n d
1 8 –2 3
2
r e c y c l a b i l i t y .
c at a l yz e t h e S uz uk i c o u p l in g o f h in de re d a ry l
N i -P d b im e t a l li c n a n o c o m p o s i t e s
( 1 m mo l ) . T h e r e s u l t i n g m i x t u r e w a s h e a t e d t o 1 5 0 °C
f o r 2 – 6 h u n d e r a r g o n . A f t e r c o m p l e t i o n , t h e r e a c t i o n
( mo n i t o r ed b y T L C ) , w a s q u e n c h e d b y a d d i t i o n o f
w a t e r . T h e a q u e o u s s o l u t i o n w a s e x t r a c t e d w i t h e t h y l
a ce t a t e ( 3 x 2 0 m L ) a n d t h e c o m b i n ed o r g a n i c e x t r a c t
w a s w a s h e d w i t h b r i n e a n d d r i e d o v e r N a S O . T h e
2 4
b r o m i d es .
P d a n d P d - N i b im e t a l li c c a t a l ys ts s u p p o rt ed o n
m u l t i - w a l l e d c a r b o n n a no t ub e s s h o w v e r y h i g h c at -
a l yt i c a c t i v i t y f o r t h e M i z o r o k i – H e c k , S u z u k i , H i y am a
2 5
2
4
a n d S o n o g as hi r a c o up l in g r e a c t io n s . T h e b i m e t a l l i c
o r g a n i c l a y e r w a s c o n c e n t r a t e d in vacuo a n d t h e c r u d e
p r o d u ct p u ri fie d b y c o l u mn c h r o m at o g r a p h y o n s i l i c a
g e l ( 1 0 0 – 2 0 0 m es h , P et ro l e u m e t h e r o r P et r o l eu m
e t h e r : 2 – 5 % E t h y l a ce t a t e) t o g i v e t h e p u re p r o d u c t .
2-Propenoic acid-3-phenyl, ethyl ester ( 2E) ( 3a)
c at a l ys i s d e s c r i b e d h a s t h e a d va nt a g e o f b e i ng l i g a n d
f r ee a s w e l l a s t h e c a t a l y s t c a n b e r e c y c l e d . A B PB I
[ p o l y (2 , 5 - b e n z i mi d a z o l e ) ] i s a h ig hl y s t a bl e p o l y m er
w i t h z e r o s o l u bi li t y i n m o s t o rg a n ic s o l v e n t s , t h u s
p r o v i di ng a r o b u s t h e t e r o g e n e o u s s u pp o r t m ed i u m
c o m p ar ab le t o i n o rg a n i c s u p p o rt s l ik e S i O , A l O , f o r
( 1 . 5 h , 0 . 1 3 1 g , 0 . 7 5 m mo l , 7 5 % y i el d , c o l o u r l es s o i l )
1
C A S R eg i s t ry N u m b e r 1 0 3 -3 6 - 6 , H N M R ( C DC l ,
2
2 3
2 6
3
b i m e t a l li c c a t a l ys ts . F u rt h e r m or e i t h a s a v er y h i g h
g l a s s t r an si t i o n t e m p e r a t u r e ( T ) * 4 5 0 °C , i n d i ca t i n g
s t ab i l i t y a t h i gh t e m p e ra t u r e s .
2 0 0 M H z , d p p m) : 7 . 7 0 ( d , J= 1 6 . 0 H z , 1 H ) , 7 . 4 7 – 7 . 6 0
( m, 2 H ) , 7 . 3 1 – 7 . 4 6 ( m, 3 H ) , 6 . 4 5 ( d , J= 1 6 . 0 H z , 1 H ) ,
g
1 3
4 . 2 8 ( q , J= 7 . 1 H z , 2 H ) , 1 . 3 5 ( t , J= 7 . 1 H z , 3 H ) ;
C
A B P B I h a s n o t b e e n s t u di e d a s a h e t e r o g e n o u s
m e d i u m f o r N P s ( n a n o p a rt i c l e s ) , b i m e t a l li c N P s o r
t r a n s i t i on m et a l c a t a ly s i s . T h e r e i s o n l y o n e r ep o r t o n
t h e u s e o f P d N P o n m e s o p o ro u s - P B I [ (p o l y (2 , 5 - b e n -
N M R ( CD C l , 5 0 M H z , d p p m ) : 1 6 5 . 9 5 , 1 4 4 . 5 8 ,
3
1 3 4 . 4 8 , 1 3 0 . 2 2 , 1 2 8 . 8 8 , 1 2 8 . 0 5 , 1 1 8 . 3 0 , 6 0 . 4 7 , 1 4 . 3 4 ;
H R M S - E SI : [ M??H ]? c al c d f o r C H O [ M ?H ]?
1 7 7 . 0 9 1 , f o u n d : 1 7 7 . 0 9 1 .
1 1 1 2
2
2 7
z i m i d a z o l e ) ] f o r t h e S u z u ki c o up l in g . T h e a c t i v a t i o n
o f a t o m e c o n o m ic a l a r y l b ro m id e s a n d c h l or i d e s i s s t i l l
a c h a l l en gi n g t a s k i n t he M i z o r o k i – H ec k r e a c t i o n a n d
r e l a t e d c r o s s c o u p l in gs . S e ve ra l s o l ut i on s h a v e b e e n
a r r i v ed a t t h i s a c t i va ti o n o f a r y l b ro m id e s u s i n g
2 . 2 Procedure for recycle study of catalyst (Ni-
Pd-ABPBI)
2 8
l i g a n d s a n d a d d i t i ve s . B i m e ta ll i c c a t a l ys ts h a v e b e e n
s h o w n t o c a t a l y z e t he a r y l b r o m id e a c t iv a t i o n i n t h e
3
S o n o g a sh i r a c o up l in g . T h e h y b r i d n o b le m et al
T o a s o l u t i o n o f N i - P d - A BP B I ( 0 . 0 5 0 g , 0 . 1 7 8 m m o l )
i n 5 m L s o l v e n t ( PE G -4 0 0 ) w a s a d d e d 4 - i o d o a n i s o l e
( 1 m mo l ) , s t y r en e ( 1 m mo l ) a n d b a s e , C y N Me
2
m e r g e d w i t h n o n -n o b l e m e ta l n a n o a l l oy s P d / C u , C o ,
N i , F e h e t e r og en iz e d o n p o l y m e rs , g r a p h e n e o r t i t a n i a
d e mo n st r a t e a n e n ha nc e m e n t i n s p e c i fi c p r o pe r t i es d u e
( 1 m mo l ) . T h e r e s u l t i n g m i x t u r e w a s h e a t e d t o 1 5 0 °C
f o r 2 – 6 h u n d e r a r g o n . A f t e r c o m p l e t i o n , t h e r e a c t i o n
( mo n i t o r ed b y T L C ) , w a s fi l t e r e d t o r e co v er t h e c a t a -
l y s t a n d t h e fi l t r a t e q u e n c h e d b y a d d i t i o n o f w a t e r . T h e
a q u e o u s s o l u t i o n w a s e x t r a c t e d w i t h e t h y l a ce t a t e ( 3 x
2 0 m L ) a n d t h e c o m b i n ed e x t r a c t w a s w a s h e d w i t h
b r i n e a n d d r i e d o v er N a S O . T h e o r g a n i c l a y e r w as
c o n c e n t r a t e d in vacuo a n d t h e c r u d e p r o d u ct p u r i fi e d
b y c o l u mn c h r o m at o g r a p h y o n s i l i c a g e l ( 1 0 0 – 2 0 0
m es h , P et ro l e u m e t h e r ) t o g i v e t h e p u re p r o d u c t . T h e
r e co v er e d c at al y s t w a s t h en a d d e d t o a f r es h s o l u t i o n
2 9 – 3 2
t
o
s
y
n
e
r
g
i
s
m
.
B a s e d o n t h e s e o b s e r v a ti o n s w e
d e s i g n e d t h e b i m e t a l l ic n a n o a l l o y s o f C u -P d a n d N i -
P d h e t e r og en iz ed o n t he f un c t io na l A B P B I p o l y m er .
T o c o n s e r v e t h e u s a g e o f e x p e n s i v e n o b l e m e t al P d ,
t h e h y b r i d s t r u c t u r e a l l oy e d b y P d a n d n o n -n o b l e ( N i ,
C u ) m e t a l s w a s d e s i g n e d a n d s y nt h e s i z e d . T h e a t o m
e co n o m ic al a r y l b r o m id e a c t iv a t io n w i th t hi s c a t a l y s t s
w a s a l s o e x p l o r e d .
2
4

J. Chem. Sci. ( 2 0 2 1 ) 1 3 3 : 8
P a g e 3 o f 1 2
8
o f t h e r e a c t i o n m i x t u re a n d t h e p ro c e s s r e p e a t e d f o r 4
m o r e t i me s ( 5 c y c l e s ) .
C u ( O A c) b y r ed u c t i o n w i t h N a BH i n t h e p r e s en c e o f
2
4
A B PB I ( 1 : 1 0 : 1 0 ) ( Sc h e m e 1 ) . T h e c at al y s t s w er e
c h a r ac t e r i z ed b y X R D , X P S, T E M , F E S E M m e t h o d s
( Fi g u r e s 1 , 2, 3, 4, 5 , 6 ) .
A4 Benzene, 1-methoxy-4-[(1E)-2-phenylethe-
nyl]-(E) (3d) ( 1 . 7 5 h , 0 . 19 1 g , 8 9 % , 0 . 89 m m o l , W h i t e
s o l i d , M . p . -1 3 6 °C ) C A S R e gi s t ry N u m b e r 1 6 9 4 - 1 9 -
T h e s y n t h e s i ze d c at a l y s t s w e r e a n a l y s ed b y X RD .
F i g u r e 1 r e p r es e n t s t h e X R D o f P d - Cu a n d P d - Ni
b i me t a l l i c c at a l y s t s l o ad ed o n p o l y m e ri c P B P B I . I t
r e v e al s t h at P d - Cu / A B PB I s h o w b e t t er c r y s t a l l i n i t y
t h an P d - N i / A B P BI . P d - Cu / A B PB I s h o w s p e a k s a t
2 h= . 4 2 . 4 5 ° ( 1 1 1 ) a n d 7 4 . 2 1 ° ( 2 2 0 ) c o r re s p o n d i n g t o
t h e m et al l i c C u w i t h J C PD S # 8 5 - 1 2 3 6 ( Su p p l em en t a ry
1
5 H N M R ( C H L O R O F O RM -d , 2 0 0 M H z , d p p m ) :
7 . 3 1 –7 . 6 9 ( m , 7 H ), 7 . 17 ( d, J= 7 . 5 H z , 2 H ) , 7 . 0 5 ( d ,
1 3
J= 8 . 7 H z , 2 H ) , 3 . 9 7 ( s , 3 H ); C N M R ( C H L O R O -
F O R M - d , 5 0 M H z , d p p m ) : 1 5 9 . 4 , 1 3 7 . 7 , 1 3 0 . 2 , 1 2 9 . 5 ,
1 2 8 . 7 , 1 2 8 . 4, 1 2 8 . 4 , 1 2 8 . 3, 1 2 8 . 2, 1 2 7 . 8, 1 2 7 . 7 , 1 2 7 . 3 ,
1 2 6 . 7 , 1 2 6 . 3 , 1 1 4 . 2 , 1 1 3 . 6, 1 1 3 . 0, 7 7 . 7 , 7 7 . 1 , 7 6 . 5 ,
5 5 . 4 ; I R ( c m -1) 3 0 1 7 , 2 9 2 5 , 2 8 5 0 , 1 6 0 2 , 1 5 1 0 , 1 4 5 2 ,
1 2 9 8 , 1 2 5 3 , 1 2 1 8 , 1 1 7 7 , 1 1 1 3 , 1 0 3 0 , 9 6 7 , 9 0 6 , 8 1 9 ,
3 4
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M o s t i n t e n s e p e a k w a s o b s er v ed a t 2 h= 3 6 . 3 5 °
w h i ch s h o w s t h at C u O p h a s e i s a l s o p r e s en t i n
b i me t a l l i c c o m p o s i t e . I n t e r e s t i n g l y a d i ff e r en t p h a s e o f
7 6 1 , 6 8 7 ; H R M S- E S I: [ M??H ]? c a l c d f o r C H O ,
1
5
1
5
2
1
1
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1
1
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d
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2
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C u P d O w a s o b s er v ed w i t h 2 h v a l u e o f 2 9 . 8 6° a n d
2
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6 1 . 3 7 . P re s e n c e o f O x y g e n h a v i n g d i ff e r en t e n v i -
r o n m e n t i n X P S c o n fi r m t h i s fi n d i n g w h i ch a l so s u g -
g e s t s a b o u t t h e h a r mo n i u s i n t e ra c t i o n b e t w e e n b o t h P d
a n d C u . P d w a s n o t o b s er v e d c l e a rl y i n X R D b e c a u se
2 . 3 General procedure for Ni-Pd-ABPBI
catalyzed Suzuki coupling of aryl iodides
T o a s o l u t i o n o f a r y l i o d i d e ( 0. 5 m m o l ), a r y l b o r o n i c o f i t s l e s s c o n c e n t r a t i o n i n t h e c o m p o s i t i o n . I n c a se o f
a ci d ( 0 . 6 m m o l ) , T B A B r ( 0 . 5 m m o l ) a n d b a s e , K P O
P d - N i / A B P BI t h er e w a s a n i n s t r u m en t a l e r ro r d u e t o
3
4
( 0 . 6 m m o l ) i n 1 0 m L s o l v e n t D i ox a n e : W a t e r ( 1 : 1 ) w h i ch t h e p e a k s h a v e b e e n s h i f t e d b y t h e v a l u e o f -3°.
w a s a d d e d N i - P d- A B P B I ( 0. 0 2 5 g , 0 . 08 5 m m o l ) . T h e 3 p r o m i n e n t p e a k s w e re o b s er v e d a t 2 h v a l u e o f 2 6 . 5 1 °
r e s u l t i n g m i x t ur e w a s h e a t e d t o 1 2 0 °C f o r 2 – 2 . 5 h ( 2 9 . 5 1 ) , 4 0 . 3 6° ( 4 3 . 3 6°) a n d 4 7 . 0 5 ° ( 5 0 . 0 5°) . L o w e r
u n d e r a r g o n . A f t e r c o m p le ti o n , t h e r e a c t io n ( mo n i - 2 h v a l u e i . e. , 2 9 . 5 1° r ep re s en t s N i O ( 0 0 2 ) w h e r e a s t h e
2
t o r e d b y T LC ) , w a s q u e n c h e d b y a d di t i o n o f w a t e r . o t h e r t w o c an b e b e c au s e o f m et al l i c N i a s r e p o rt ed
T h e a q u e o u s s o l u t i on w a s e x t ra c t e d w i t h e t h yl a ce t at e e l s e w h e r e. 1 1 1 a n d 2 0 0 p l an e o f m et al l i c N i a r e r e p -
( 3 x 2 0 m L ) a n d t he c o m b in e d o rg a n ic e x t ra c t w a s r e s en t e d b y 2h = 4 3 . 3 6 ° a n d 5 0 . 0 5 ° c o r r es p o n d i n g t o
w a s h e d w i t h b r i n e a n d d r i e d o v e r N a S O . T h e J C PD S # 7 0 - 0 9 8 9 .
2
4
o r g a n i c l a y e r w a s c o nc e n t ra t e d i n v a c u o a n d t h e c ru d e
F i g u r e 2 r e p r es e n t s t h e S E M - E D X o b s er v at i o n s o f
p r o d u c t p u r i fie d b y c o l um n c h ro m a to gr a p h y o n s i l i c a P d - N i / A B P BI . T h e m i c ro g r ap h s u g g e s t s r o u n d m o r -
g e l ( 1 0 0 – 2 0 0 m es h , P e t ro le u m e t h e r ) t o g i v e t h e p u r e p h o l o g y o f p a r t i c l es d i s t r i b u t e d i n p o l y m e ri c s u p p o r t
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a t a r o u n d 5 0 0 n m s c a l e . E D X p a t t er n i s a l s o i n
1,10-Biphenyl (6a) ( 2 h , 0 . 0 6 7 g , 0 . 4 3 5 m m o l , 8 7 % c o h e r en ce w i t h o u r c al cu l a t e d v a l u e o f P d a n d N i .
y i e l d , w h i t e s o l id , M . p . -6 8 °C ) C A S R e g i s t r y S i m i l a r o b s er v a t i o n s w e re s e e n i n S E M - E D X p a t t e r n
1
N u m b e r 9 2 - 5 2 - 4 H N M R ( 20 0 M H z , C D C l , d p p m) o f P d - Cu / A B PB I a s r e p r es e n t ed i n F i g u re 3 .
3
– 7 . 62 –7 . 5 6 ( m , 4 H ) , 7 . 49 – 7 . 3 ( m , 6 H ) I R ( c m -1 )
H e re d i s p e r s i o n o f m et al l i c p a r t i cl es w a s f o u n d i n
– 3 3 8 3 , 2 9 6 5 , 2 7 2 5 , 1 9 4 7 , 1 8 7 9 , 1 7 1 1 , 1 5 7 0 , 1 4 5 7 , f o r m o f a g g r e g a t e d c l u s t e rs w h i ch c an b e t h e r e a so n o f
1 3 7 4 , 1 3 0 7 , 1 1 6 3 , 1 0 8 0 , 9 6 8 , 7 2 9 ; H R M S - E S I: m o r e c r y s t a l l i n i t y o b s er v e d i n X R D t h an P d - Ni /
[ M ] ? c a l c d f o r C H [ M ] ? 1 5 4 . 0 7 8, f o u nd : 1 5 4 . 0 7 8 A B PB I . I n o r d e r t o fi n d o u t t h e p a r t i c l e s i z e a n d
1 2 1 0
i n t e n s i t y o f d i s p e r s i o n T E M i m a g i n g w a s p e r f o r m ed .
F i g u r e 4 r e p r es e n t s a c o m b i n e d i m a g e o f b o t h P d - Ni /
A B PB I a n d P d - Cu / A B PB I w i t h T E M - E D X .
3. Results and Discussion
T h e b i m e t a l li c n a no a l l oy c a t a l ys ts w e r e p re p a r e d b y
t h e s i m u l t an eo us r e d u c ti on o f a m i x tu re o f c o p p e r
a ce t a t e o r n i c k e l a c e t a t e , p a l la di u m a c e t a t e a n d p o l y -
m e r A B P B I , i n e t h y le ne g ly c o l o r D M S O a s s o l v e n t ,
3 . 1 EDX pattern followed by atomic and weight
percent of Pd and Ni on ABPBI
3 3
u s i n g N a B H . N i -P d w a s p re p a r e d b y t h e N a BH
S p h e r i c a l p a r t i cl e m o r p h o l o g y w a s a l s o c o n fi r m e d b y
r e d u c t i o n o f a m i x t ur e o f P d (O A c ) a n d N i (O A c) i n T E M i m a g i n g . A g g r e g a t i o n o f c l u s t e rs w a s o b se r v e d
4
4
2
2
t h e p r e s e n ce o f A B P B I , i n a 1 : 1 0 : 2 0 r a t io . S i m i l a r l y , i n b o t h P d - Cu / A B PB I a n d P d - N i / A B P BI c a t a l y st s .
C u - P d w a s p r e p a r e d f ro m a m i x t u re o f P d (O A c ) a n d A f t e r c al cu l a t i o n o f 5 0 n a n o p ar t i c l e s t h e s i ze o f P d - Ni /
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J. Chem. Sci. ( 2 0 2 1 ) 1 3 3 :8
Scheme 1. B i m e t a l li c N P C a t a l y s t P r e p a r a t i o n & S t r u c t u r e .
A B PB I w a s o b s er v e d a ro u n d 6 . 6 8 n m w h e r e as t h e s i z e
o f P d - Cu / A B PB I w a s 4 . 4 7 n m .
T h e F E S E M d a t a s h o w s c l e a rl y C u - Pd b i m e t a l l i c
n a n o c l u s t e rs a d h e r i n g t o t h e s u r f a ce o f t h e p o l y m e r
s u p p o r t . T h e a g g r e g a t e d c l u s t e rs a re o f n o n - u n i f o r m
d i s t r i b u t i o n w i t h s i ze s o f a r o u n d 5 0 0 n m . T h e N i - Pd
o n t h e o t h e r h a n d a r e e mb ed d e d i n t h e p o l y m e r s u p -
p o r t w i t h a m i c ro p o ro u s n a t u re . T h e p o l y m e r s u r f ac e
i s b r o k en . T h e F E S E M E D A X s h o w s r at i o o f C u : Pd i s
6 . 5 : 1 w h i l e N i : Pd i s 5 . 1 : 1 . T h e T E M d a t a s h o ws p o l y
d i s p e r s ed C u - Pd b i me t a l l i c n a n o p a r t i c l es w i t h a s i z e
d i s t r i b u t i o n o f 3 . 5 n m t o 5 . 8 n m . T h e N i - P d i s a l s o
p o l y d i s p e r s ed w i t h a s i ze d i s t r i b u t i o n r a n g i n g f r o m
3 . 5 n m t o 8 . 9 n m .
S y n t h e s i s o f m et al - me t a l o x i d e n a n o h y b r i d p a i r s
w a s c o n c l u d ed b y X P S a n a l y s i s o f o u r s c r ee n e d c a t -
Figure 1. X R D p a t t e r n o f P d - C u a n d P d - N i b i m e t a l l ic
c a t a l y s t s s u p p o r t ed o n A B P B I .
Figure 2. S E M - E DX o f P d - Ni / A B P B I . ( a) S E M i m a g e a t 3 0 lm ( b) S E M i m a g e a t 5 0 0 n m ( c) E D X p a t t e r n f o ll o w ed b y
a t om ic a n d w e i g h t p e rc e n t o f P d a n d N i o n A B P B I .

J. Chem. Sci. ( 2 0 2 1 ) 1 3 3 : 8
P a g e 5 o f 1 2
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Figure 3. S E M - E DX o f P d - C u / A B P B I . ( a) S E M i m a g e a t 5 lm ( b) S E M i m a g e a t 1 lm (c) .
a l ys t s ( F i g u r e s 5 , 6) . B o th t h e P d -C u / A B P BI a n d P d - w e re c o n s u me d i n s h o r t r e ac t i o n t i me s a n d t h e y i e l d s
N i / A B PB I s h o w s p r e s e n c e o f P d a n d P d O a t t h ei r w e re m o d e r at e.
r e s p e c t i v e b i n di n g e n e r g y i.e. *3 3 5 e V a n d *3 4 0 e V,
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r e s p e c t i v el y . M e t a l li c C u w a s o b s e rv e d a r o u n d 9 3 2 . 3 3 g a v e g o o d r es u l t s w i t h r e co v er a b i l i t y o f t h e p o l y m e r
e V . P r e s en ce o f s t r on g s a t e l l it e p e a k s i n C u d e c o n - s u p p o r t e d c at a l y s t b y s i mp l e fi l t r a t i o n a ft e r t h e r e a c-
v o l u t i o n a l s o r e v e a le d t he e x i s t e n c e o f C u -C u O p a i r .
t i o n w a s c o m p l e t e . R ec y c l e s t u d i e s o f t h e c at a l y st f o r
T h e s e t r e nd s c o n t i n u e d i n t he c a s e o f N i a l s o w h e r e t h e M i z o r o k i – H ec k r ea c t i o n o f 4 - i o d o a n i s ol e w i t h
d i f f e r e n t t y pe s o f o x i d e s c o e x is t w i th m e ta ll i c N i w i t h s t y r en e w a s c ar r i e d o u t . T h e c at al y s t w a s a ct i v e e v e n
s l i g h t s h i f t i n B E d u e t o q u a n t u m s i z e e f f e c t a r o u n d a t a f t e r 5 r e cy cl es g i v i n g h i g h y i el d s ( 6 2 % t o 9 7 % ) i n
8 5 6 – 8 6 4 e V . T h e n a t ur e o f C a rb on a n d O x y g e n s u r - e ac h c y c l e ( T a b l e 2) .
f a c e w a s f o u n d a l m o s t s i m i l a r i n b o t h t he c a s e s a s t h e L e a ch i n g s t u d i e s w a s a l s o c ar r i e d o u t w i t h t h e N i -
s u p p o r t s y s t e m w a s s a m e . S t r o n g p r o of s o f a ro ma t i c P d - A BP B I c at al y s t . A b l an k r ea c t i o n w a s c ar r i e d o u t
c o n j u ga te d c a r b o n b o n d e d w i t h - N H g ro u p a n d w i t h o u t a l k e n e f o r 6 h a t 1 5 0 °C . T h e c at al y s t w a s t h e n
2
f r am e wo r k N - C = O w a s t h e re w i th C 1 s d e c o n v o l u t i o n fi l t e r e d o f f a n d s t y r en e a d d e d t o t h e fi l t r a t e w h i c h w as
a t t h e B . E . o f 2 8 5 a n d 2 8 8 e V .
t h en a g a i n h e a t e d t o 1 5 0 °C i n a n o i l b a t h . M o n i t o r i n g
S i m i l ar ly l a t t i c e o x y g e n , l a t e r a l o x y g e n w i t h d i f- b y T L C s h o w ed f o r ma t i o n o f p r o d u c t . T h e r e a ct i o n
f e r e n t c h e m i c al e n v i r on m e n t a n d a d s o rb e d o x y g e n t o o k a l o n g e r 2 3 h f o r c o m p l e t i o n w i t h 6 3 % y i e l d o f
w a s o b s e r v e d a t *5 3 0 , 5 3 1 a n d 5 3 3 e V , r e s p e ct i v e l y . t h e M i z o r o k i – H ec k r ea c t i o n p r o d u c t . T h i s s h o w s s o m e
T h e p r e s e n ce o f m e ta l -m e ta l o x i d e s n a n o p a i r s a n d l e a ch i n g o f t h e c at al y s t .
t h e i r c o m p l e x m u t u a l e l e c t ro n i nt e r a c ti o n c a n b e o n e
o f t h e r e a s o n s f o r e x c e l le n t a c t iv i ty o f o u r c a t a l y s t s .
T h e r e ac t i o n o f a ry l b r o m i d e s w i t h N i - P d - A B P BI
c at al y s t g a v e v e r y l o w y i el d s . S o w e t r i ed u s i n g C u -
V a r i ou s a r y l i o di d e s g a v e h ig h y i e ld s f o r t h e P d - A BP B I a s c at a l y s t ( Sc h e m e 3 ) . C u - Pd - A B PB I
M i z o r o k i –H e ck r e a c t i on , u s i n g N i -P d - A B P B I a s c at - s h o w ed m o d e r at e a ct i v i t y f o r t h e M i z o r o k i – H e c k
a l ys t , w i t h s t y r e ne a n d e t h y l a c ry l a t e , i n s h or t r e a ct i o n r e ac t i o n o f a r y l b r o m i d e s ( T a b l e 3 ) . 4 - B ro mo a n i s o l e
t i me s ( S c h e me 2) ( T a b l e 1 ) . H e r e , C y N M e w a s t h e s h o w ed g o o d a ct i v i t y w h i l e t h e o t h e r b r o m i d e s g a v e
2
b a s e o f c h o i c e w h il e K C O a n d N a O A c g a v e l o w er o n l y m o d e r at e r ea c t i v i t y . A h i g h y i el d o f 8 7 % w as
2
3
y i e l d s . I n t h e r e a c t io n w i t h K C O , t h e a r y l i o d i d es o b t a i n e d i n t h e r e ac t i o n o f 2 - b r o m o b e n z a l d e h y d e w i t h
2
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Figure 4. T E M i m a g i n g o f ( a) P d - N i / AB P B I ( b) T E M - E D X o f P d - N i/ A B P B I (c) T E M - E D X o f P d - C u / A B P BI ( d) T EM
i ma g e s o f P d - Cu /A B P B I a t 5 0 n m a n d ( e) P a r t i c l e s i z e o f P d - C u a t 2 0 n m .
s t y r en e. A l l r e a c t i on s p r o c e e d e d w i t h E - s e l ec t i v i t y ,
C o mp ar i s o n r ea c t i o n s w e re c ar r i e d o u t w i t h t h e
t y p i c a l f o r t h e M i z o r o k i – H ec k r e a c t io n . T h e a t o m m o n o m e t a l l i c c at al y s t P d - A BP B I . T h i s c at a l y s t w as
e co n o m i ca l b r o m id e a c t iv a t i o n i s a c h a l l e n gi n g t a s k i n p r e p a r ed i n t h e s i mi l a r p r o c e d u r e d e s c r i b e d a b o v e .
t h e M i z o r o k i – H ec k r e a c t io n a n d r e l a t e d a r y l h a l i d e R es u l t s a re s h o w n i n t h e T a b l es 2 , 3 a n d 4. T h e
a ct i va t i o n r e a c t i o n s . L o w t o m o de ra te y ie ld s w e r e r e ac t i o n o f 4 - i o d o a n i s o l e w i t h s t y r en e g a v e 6 3 % y i e l d
o b t a i n ed i n t h e M i z o r o k i – H ec k r e a c t io n o f a r y l b r o - i n 4 . 5 h ( 1 A ) ; T h e r e ac t i o n o f 4 - b r o m o a n i s o l e w i t h
m i d e s w i t h C u - P d- A B P BI N P c a t a l y s t. T h e s e l e c t i v i t y s t y r en e g a v e 4 2 % i n 5 . 5 h ( 7 A ) a n d t h e S u z u k i c o u -
f o r t h e E - i s o m e r w a s r e t a i n e d i n t he s e r e a c t io n s a l s o . p l i n g o f i o d o b e n z e n e w i t h b e n z e n e b o r o n i c a c i d g a v e
T h e r e a c t i o n o f 4 - i od o a n i s o l e w i th s t y re n e a n d 7 8 % y i el d i n 2 . 3 h . O v e r al l , t h e m o n o m e t a l l i c c a t a l y s t
e t hy l a c r y l a t e c a t a l yz e d b y N i -P d - A B P B I w e r e a l s o g a v e l o w er y i el d s i n l o n g e r r e ac t i o n t i me s .
c ar r i e d o u t i n m o de ra te y ie ld s ( 5 5 a n d 3 4 % , r es p e c-
t i v e l y ) i n a q u e o u s m e d i a w i t h C T A B a s s u r fa c t a n t .
T h e r ea c t i o n m ec h a n i s m c o u l d b e e x p l ai n e d t h u s ;
c o - o r d i n at i o n o f n i t r o g e n o f t h e b e n z i m i d a z o le p o l y -
T h e S u z u k i c o u p l in g o f v a r io us a r y l i o d i d e s w i t h m er t o N i f o l l o w e d b y e l e ct r o n fl o w t o P d c a u se s
s e v e r a l a r y l b o r o n i c a c i d s c a t a l y z e d b y N i -P d- A B P BI i n cr e a s e i n e l e ct r o n c h a rg e d e n s i t y o n t h e P d ; r e d u ci n g
p r o c e e d ed i n h i g h t o q u a n t it a t i v e y ie ld s i n a p a r t P d ( I I) t o t h e h i g h l y a ct i v e P d ( 0 ) w h i ch t h en o x i d a-
a q u e o u s s o l v e n t s y s t e m o f d i o x a n e :w a t e r 1 : 1 t i v e l y a d d s t o t h e a r y l h a l i d e f o l l o w e d b y t h e s t a n d a r d
( S c h e m e 4 , T a bl e 4) . T h e a t t e m p t e d S o n o g as h i r a p r o t o c o l o f t h e M i z o r o k i – H ec k r ea c t i o n a n d fi n a l l y
c o u p l i n g o f 4 - i o do a n i s o l e w i t h p h e n y l a c e t y l e n e c at - e n d i n g w i t h t h e E - s u b s t i t u t e d p r o d u ct . S am e m e c h a -
a l yz e d b y N i - P d - A B P B I c a t a l y s t, g a v e t h e a l k y n e n i s m h o l d s g o o d f o r t h e h i g h y i el d i n g S u z u k i c o u p l i n g .
G l a s e r t y p e h o m o c o up li n g i n 9 2 % y i e ld .
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Figure 5. X P S p a t t e r n o f P d - C u / A B P B I (a) P d i n P d - C u / A B P B I ( b) C u i n P d - C u / A B P B I ( c) C a r b o n i n P d - C u / A B P B I a nd
( d) O x y g e n i n P d - C u / A B P B I .
a l lo y s u p p o r t ed o n A B P B I p o l ym e r a s w e l l a s t h e
r e c y c l a b i l i t y o f t he c a t a l ys t. T h i s p re l i m i n a r y c o m -
m u n i c at i on d e s c ri b e s p r o of -o f- c o n c e p t w h i l e f u t u r e
w o r k w i l l e x p e ri m e n t w i t h v a r io us r a t io s o f t h e
b i m e t a l l i c a l l o y t o i n c re a s e c a t a l y t i c a c t iv i ty .
s u p p o r t e d n a n o a l l o y c at al y s t a ct i v a t e d t h e M i z o r o k i –
H e ck a r y l a t i o n a n d S u z u k i – M i y a u r a c o u p l i n g i n v e r y
h i g h t o q u an t i t a t i v e y i el d s a n d s h o rt r ea c t i o n t i m e s.
A r y l b r o m i d e s g a v e l o w t o m o d e r at e y i el d s o f t h e
M i z o r o k i – H ec k s u b s t i t u t i o n p r o d u c t s w i t h C u - P d -
A B PB I a s c at a l y s t . A l l t h e M i z o r o k i – H ec k r e a ct i o n s
p r o c e ed ed w i t h E - s e l e c t i v i t y . R ec y c l e o f t h e c a t a l y s t
( 5 c y c l e s ) f o r t h e M i z o r o k i – H ec k r e ac t i o n o f 4 - i o d o
a n i s o l e w i t h s t y r en e w a s p o s s i b l e w i t h v e r y h i g h y i e l d s
i n e ac h c y c l e . P ro o f o f c o n c e p t o f t h e n o v el A BP B I
s u p p o r t e d b i me t a l l i c n a n o a l l o y i s d e m o n s t ra t e d w i t h
t h e a ct i v a t i o n o f t h e M i z o r o k i – H ec k r e ac t i o n a n d t h e
S u z u k i – M i y a u r a c o u p l i n g . A t t e mp t ed S o n o g a sh i r a
c o u p l i n g r es u l t ed i n G l a s e r t y p e h o mo c o u p l i n g o f t h e
t e r m i n a l a l k y n e i n v e r y h i g h y i el d s . A v a r i e t y o f h a l i d e
a ct i v a t i o n a n d o t h e r r e ac t i o n s t o b e e x p l o r ed y et , a r e
n o w f e as i b l e w i t h t h e b i me t a l l i c n a n o a l l o y h e t e r o g e -
n i ze d o n A B PB I p o l y m e r. F u r t h e r s t u d i e s w i l l e l a b o -
r at e o n t h e u s e o f t h i s p o l y m e r s u p p o r t e d c at a l y s i s i n
v a r i o u s o r g a n i c r e ac t i o n s .
4. Conclusions
I n s u m m ar y, t h e b i m e t a ll i c n a n o a l l o y a r c h i te c t u r e w a s
r e a d i l y c o n s t r u c t e d o n t h e r ob u s t A B P B I p o l y m er b y
o p e r a t i o na l l y s i m p l e a n d a m bi e n t c o n d i ti o n s . T h e
p o l y m e r s u p p o r t i s n o v e l , u n p re c e d e n te d , e x t r e me l y
s t ab l e , i n s o l u b l e i n o rg a n ic s o l v e n t s a n d f u n c t i o n s
e v e n a t h i g h o p e r a t io na l t e m p e r a t u re s w i th o u t a n y
d e g r a d a t i o n a s s o c i a t e d w i th p h o s p h i n e l ig a n d s a n d
o t h e r p o l ym e r s u pp o r t s . I t i s c o m p a r a b le w i th v a r i o u s
i n o r g a ni c s u p p o r t s l ik e S i O a n d A l O i n h e t e r o -
2
2 3
g e n e i t y a n d t h e N -c oo rd in a t i n g g r o up s o f t he p o l y me r
p r o v i de e x c e l l e n t s t a b i l iz a t io n o f t h e b im e t a l l i c n a n o
p a r t i c l e s . T h e h a r m o n i c N i -P d- A B P BI b i m e t a l l i c

8
P a g e 8 o f 1 2
J. Chem. Sci. ( 2 0 2 1 ) 1 3 3 :8
Figure 6. X P S p a t t e r n o f P d - N i / AB P B I ( a) P d i n P d - N i/ A B P B I ( b) N i i n P d - N i/ A B P BI (c) C a r b o n i n P d - N i /A B P B I a nd
( d) O x y g e n i n P d - N i / AB PB I .
I
W
Ni-Pd-ABPBI (Cat)
+
W
Cy2NMe, PEG-400
Argon, 150 oC
R
R
Yield : 58 - 89 %
R : H, 4-CH3O, 4-CF3O, 4-F, 4-Cl, 4-CH3, 2-CH3, 2,4-F
W : COOC2H5, C6H5
Scheme 2. N i - Pd – A B P B I c a t a l y s i s o f t h e M i z o r o k i – H e c k r e a c t io n o f a r y l i o d i d e s .

J. Chem. Sci. ( 2 0 2 1 ) 1 3 3 : 8
Table 1. N i - P d - A B P B I c a t a l y s i s o f t h e M i z o r o k i – H e c k r e a c t io n o f a r y l i o d i d e s .
P a g e 9 o f 1 2
8
a
T i m e
h
S l. n o :
A r y l I o d i d e
C H I
C H I
A l k e n e
B a s e , S o l v e n t
Y
i
e
l
d
P
r
o
d
u
c
t
,
E
:
Z
r
a
t
i
o
1
2
3
4
5
6
7
8
E t h y l a c ry l a t e
S t y re n e
E t h y l a c ry l a t e
S t y re n e
S t y re n e
E - C i n n a m a l d e h y d e
E t h y l a c ry l a t e
E t h y l a c ry l a t e
S t y re n e
S t y re n e
S t y re n e
E t h y l a c ry l a t e
C y N M e , P E G - 4 0 0
2
C y N M e , P E G - 4 0 0
2
1 . 5
2 . 5
2 . 2 5
1 . 7 5
2
7 5
5 8
6 6
8 9
7 8
5 0
8 5
8 8
8 9
8 6
7 0
8 2
E
E
E
E
E
6
5
6
5
4 - C H O . C H I
6 4
N a O A c , P E G - 4 0 0
K C O , P E G - 4 0 0
C y N M e , N M P
3
4 - C H O . C H I
3 6 4
2
3
4 - C H O . C H I
4
3
6
2
b
4 - C H O . C H I
6 4
N a O A c , P E G - 4 0 0
C y N M e , P E G - 4 0 0
1 6
E
3
4 - C F O . C H I
3
1 . 1 0
1 . 1 0
1 . 4 5
1 . 2 5
2 . 3 5
1 . 1 0
E
E
E
E
E
E
6
4
2
4 - F . C H I
6
C y N M e , P E G - 4 0 0
2
C y N M e , P E G - 4 0 0
2
C y N M e , P E G - 4 0 0
2
C y N M e , P E G - 4 0 0
2
4
9
4 - C l . C H I
6
4
1 0
1 1
1 2
4 - C H . C H I
4
3
6
2 - C H . C H I
3
6
4
2 , 4 - F . C H I
4
C y N M e , P E G - 4 0 0
2
6
a : R e ac t io n c on di t i o n s : A rI ( 1 m m o l ) , A l k e n e ( 1 – 2 m m o l ) , C y N M e ( 1 E q ) , C a t - N i - P d - A B P B I ( 0 .0 5 g , 0 . 1 7 8 m m o l ) , P E G -
2
4 0 0 , A r g on , 1 5 0 °C , b : S a m e c o n d i t i o n s ? T B A B r ( 1 m m o l ) .
a
Table 2. N i - P d - A B P B I N P c a t a l y s i s o f M i z o ro k i – H e c k r e a c t io n o f 4 - io d o a n i s o l e – R e c y c le s t u d y .
S . n o
A r y l H a l i d e
A l k e n e
B a s e , S o l v e n t
T i m e h
Y i e l d %
P r o d u c t E : Z, r at i o
E
1
1 A
2
3
4
4 - C H O . C H I
4
S t y re n e
S t y re n e
S t y re n e
S t y re n e
S t y re n e
S t y re n e
C y N M e , P E G - 4 0 0
2
C y N M e , P E G - 4 0 0
2
C y N M e , P E G - 4 0 0
2
C y N M e , P E G - 4 0 0
2
C y N M e , P E G - 4 0 0
2
C y N M e , P E G - 4 0 0
2
3
4 . 5
7
5
2 . 5
4 . 5
8 9
6 3
6 2
9 7
8 0
8 3
3
6
b
4 - C H O . C H I
3
E
6
4
4 - C H O . C H I
3
E
E
E
E
6
4
4 - C H O . C H I
4
3
6
4 - C H O . C H I
4
3
6
5
4 - C H O . C H I
3
6
4
a : R e a ct io n c o nd i t i o n s : A rI ( 1 m m o l ) , A l k e n e ( 1 m m o l ) , C y N M e ( 1 E q ) , C a t - N i - P d - A B P B I ( 0 .0 5 g , 0 . 1 7 8 m m o l ) , P E G -
2
4 0 0 , A r g on , 1 5 0 °C , b : A l l c o n d i t i o n s s a m e w i t h M o n o m e t a l l ic c a t a l y s t – P d - A B P B I .
Br
W
Cu-Pd-ABPBI (Cat)
NaOAc, PEG-400
TBABr, Ar150 oC
+
W
R
R
29 - 87 % yield, E-
R : 4-CH3O, 4-CH3, 2-CHO, C10H7, 4-C6H5
W : COOC2H5, C6H5
Scheme 3. C u - Pd -A B P B I c a t a l y si s o f t h e M i z o r o k i – H e c k r e a c ti o n o f a r y l b r o m id e s .

8
P a g e 1 0 o f 1 2
J. Chem. Sci. ( 2 0 2 1 ) 1 3 3 :8
a
Table 3. C u - P d - A B PB I N P c a t a l y s i s o f t h e M i z o r o k i – H e c k r e a c ti o n o f a r y l b r o m id e s .
S . n o
A r y l H a l i d e
A l k e n e
B
a
s
e
,
S
o
l
v
e
n
t
T i m e h
Y i e l d %
P r o du c t
1
2
3
4
5
6
7
7 A
8
4 - C H O . C H B r
3
S t y re n e
S t y re n e
E t h y l a c ry l a t e
S t y re n e
S t y re n e
E t h y l a c ry l a t e
S t y re n e
S t y re n e
S t y re n e
S t y re n e
N a O A c , D M F
N a O A c , P E G - 4 0 0
C y N M e , P E G - 4 0 0
2
7 2
6 5
3 5
2 8
8 7
7 4
3 3
5 9
4 2
2 9
3 7
4 5
3 5
2 5
E
E
E
E
E
E
E
6 4
4 - C H . C H B r
3
1 . 5
3 . 1 5
7 . 2 5
5
6 4
4 - C H . C H B r
4
3
6
2 - C H O . C H B r
6
N a O A c , P E G - 4 0 0
N a O A c , P E G - 4 0 0
N a O A c , P E G - 4 0 0
N a O A c , P E G - 4 0 0
N a O A c , P E G - 4 0 0
N a O A c , N M P
N a O A c , P E G - 2 0 0
N a O A c , P E G - 4 0 0
N a O A c , P E G - 4 0 0
N a O A c , P E G - 4 0 0
4
1 - B r - N a p
1 - B r - N a p
4 - C H O . C H B r
1 2
9 . 5
5 . 5
2 8
2 8
1 9
3
6
4
b
4 - C H O . C H B r
3
E
6 4
4 - C H O . C H B r
3
E
E
E
E
E
6 4
9
4 - C H O . C H B r
3
6
4
1 0
1 1
1 2
4 - B r - B i p h
4 - C H . C H B r
S t y re n e
S t y re n e
S t y re n e
1 . 5
2
3
6 4
4 - C l . C H B r
4
6
a
R e a ct i o n c on di t io n s : A rB r ( 1 m m o l ) , A l k e n e ( 1 – 2 m m o l ) , N a O A c ( 1 E q ) , T B A B r ( 1 m m o l ) , C a t - C u - P d - A B P B I ( 0. 0 5 g ,
0 . 1 7 5 m m o l) , P E G - 4 0 0 , A rg o n , 1 5 0 °C , b : A l l c o n d i t i o n s s a m e w i t h M o n o m e t a l li c c a t a l y s t – P d - A B P B I .
I
Ni-Pd-ABPBI (Cat)
Ar
Ar.B(OH)2
+
K3PO4, TBABr
R
R
Dioxane : H2O (1:1)
84 - 100 % yield
120 oC
Argon
R : H, 4-CH3, 4-Cl, 4-OCH3
Ar- C6H5, 4-CH3C6H4, 4-CH3O.C6H4, 4-ClC6H4, 1-Nap
Scheme 4. N i - P d - AB P B I c a t a l y s i s o f t h e S u z u k i c o u p l i n g o f a r y l i o d i d e s .
a
Table 4. N i - P d - A B P B I N P c a t a l y s i s o f t h e S u z u k i c o u p l i n g o f a r y l i o d i d e s .
S . n o
A r y l H a l i d e
A ry l b o r o n i c a c i d
C H B ( O H)
C H B ( O H)
P r o d u c t
T i m e h
Y i el d %
8 7
7 8
8 4
9 4
1
1 A
2
3
4
5
6
7
8
C H I
6
C H . C H
6 5
C H . C H
6 5
2
5
6
5
2
2
6
5
b
C H I
6
2 . 3 0
2 . 5
2
2 . 5
1 . 5
2
2 . 1 5
2
1 . 5
2
5
6
5
6
5
C H I
6
4 - C H O . C H B ( O H )
3
4 - CH O . C H . C H
6 5
5
6
4
2
3
6
4
4 - C H . C H I
3
C H B ( O H)
6
4 - CH . C H . C H
6 5
6
4
5
2
3
6
4
4 - C H . C H . I
3
4 - C l . C H B ( O H )
6
4 - Cl . C H . C H . CH - 4 0
4 - Cl . C H . C H
9 5
6
4
4
2
6
4
6
4
3
4 - C l . C H . I
6
C H B ( O H)
6
1 00
1 00
1 00
9 2
1 00
9 8
5
5
2
6
4
6
5
4 - C l . C H . I
6
4 - C H . C H B ( O H )
3
4 - Cl . C H . C H . CH - 4 0
4
6
4
2
6
4
6
4
3
4 - C H O . C H I
6
C H B ( O H)
6
4 - CH O . C H . C H
6 5
3
4
5
2
3
6
4
4 - C H O . C H I
4
4 - C H O . C H B ( O H )
4
4 - CH O . C H . C H O C H - 4 0
1 - N a p - C H . O C H - 4
3
6
3
6
2
3
6
4
6
4
.
3
9
1 0
4 - C H O . C H I
6
1 - N a p - B ( O H)
C H B ( O H)
3
4
2
6
4
3
b
4 - C H O . C H I
6
4 - CH O . C H . C H
3 6 4 6 5
3
4
6
5
2
a - R ea c ti o n c o nd i t i o n s : A rI ( 0 . 5 m m o l ) , A ry l b o r o n i c a c i d ( 0 .6 m m o l ) , T B A B r ( 0 .5 m m o l ) , K P O ( 0 .6 m m o l ) , C a t -N i- P d-
3
4
A B P B I ( 0 . 0 25 g , 0 . 0 8 9 m m o l ) , d i o x a n e : w a t e r 1 : 1 ( 1 0 m L ) , A r g o n , 1 2 0 °C ; b - A l l c o n d i t io n s s a m e w i t h M o n om et a ll i c
C a ta l ys t P d - A B P B I , b - S a m e r e a c t i o n c o n d i t i o n s w i t h C a t a ly s t C u - P d - A B P BI ( 0 .0 2 5 g , 0 . 0 8 7 5 m m o l ) .

J. Chem. Sci. ( 2 0 2 1 ) 1 3 3 : 8
P
a
g
e
1
1
o
f
1
2
8
1 3 . I y e r S a n d T h a k u r V V 2 0 0 0 T h e n o v e l u s e o f N i , C o ,
C u a n d M n h e t e r o g e n e o u s c a t a l y s t s f o r t h e H e c k
r e a c t io n J. Mol. Catal. A Chem. 157 2 7 5
1 4 . H a n d a S , S l a c k E D a n d L i p s h u t z B H 2 0 1 5 N a no n -
i c k e l - c a t a l y z e d S u z u k i– M i y a u r a c r o s s - c o u p l i ng s i n
w a t e r Angew. Chem. Int. Ed. 54 1 1 9 9 4
Supplementary Information (SI)
S u p p l e m en t a r y i n f o r m a t i o n i s a v a i l a b l e a t w ww . i a s . a c .i n /
c h e m s ci .
Acknowledgements
1 5 . Y a o Q , K i n n e y E P a n d Y a n g Z 2 0 0 3 L i g a n d - f r ee H e ck
r e a c ti o n : P d ( O A c ) a s a n a c t i v e c a t a l y s t r e v i s i t ed J.
Org. Chem. 68 7 5 2 8
U K K t h an k s t h e B R N S f o r fi n a n c i a l s u p p o r t , p r o j e c t G A P-
3 1 9 3 2 6 a nd V P P a P A- I I p o s t . W e a l s o t h a n k D r . C V R o d e
f or a s si s t a nc e w i t h t h e c a t a l y s t c h a r a c t e r i z a t i o n .
2
1 6 . B o z e l l J J a n d V o g t C E 1 9 8 8 B im e t a l li c c a t a l y s i s . A
n e w m e t h o d f o r t h e a c t i v a t io n o f c h l o r o a r e n e s t ow ar d
p a l l a d i u m - c a ta l y z e d c o u p l i n g w i t h o l e fi n s J. Amer.
Chem. Soc. 110 2 6 5 5
Conflict of interest T h e r e a r e n o c o n fl i c t s t o d e c l a r e .
1 7 . S a r k a r S M , U o z u m i Y a n d Y a m a d a Y M A 2 01 1 A
h i g h l y a c t i v e a n d r e u s a b l e s e l f - a s s e m b l e d p o l y ( i m i d a-
z o l e / p a l la d iu m ) c a t a l y s t : A l l y l i c a r y la ti o n / a l k en y l at i o n
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4 . F e n g L , C h on g H , L i P , X i a n g J , F u F , Y a n g S , Y u H ,
S h e n g H a nd Z h u M 2 0 1 5 P d – N i a l l o y n a n o p a r t ic l e s a s
e f f e ct i v e c at a ly s t s f o r M i y a u ra – H e c k c o u p l i n g r e a c ti o n s
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5 . R ai R K , T y a g i D , G u p t a K a n d S i n g h S K 2 0 1 6
A c t iv at e d n an os t r u c t u r e d b i m e t a l l i c c a t a l y s t s f o r C – C
c ou pl i n g r e ac t i o n s : r e c e n t p r o g r e s s Catal. Sci. Technol.
6 3 3 4 1
6 . R ee t z M T , B r e i n b a u e r R a n d W a n n i n g e r K 1 9 9 6
S u zu k i a n d H e c k r e a c t i o n s c a t a l y z e d b y p r e f o r m e d
p al l a d iu m c lu s t e r s a n d b i m e t a l l i c c l u s t e rs Tetrahedron
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2 4 . S e t h K , P u r o h i t P a n d C h a k r a b o r ti A K 2 0 1 4 C o o p er -
a t i v e c a t a l y s i s b y p a l l a d i u m – n ic k e l b i n a r y n a n o cl u s t e r
f o r S u z u k i– M i y a u r a r e a c ti o n o f o r th o - h e t e r o c yc l e - t et h -
e r e d s t e r i c a l l y h i n d e r e d a r y l b r o m i d e s Org. Lett. 16
2 3 3 4
2 5 . O h ta k a A , S a n s a n o J M , N a j e r a C , M i g u e l - G a rc i a I ,
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P a l la d iu m a n d b i m e t a l l ic p a l l a d i u m – n i c k e l n a no p a r t i-
c l e s s u p p o r t e d o n m u l t iw a l l e d c a r b o n n a n o t u b e s : a pp l i -
c a t i o n t o c a r b o n – c a r b o n b o n d - f o r m i n g r e a c t i on s i n
w a t e r ChemCatChem. 7 1 8 4 1
2 6 . K u mb h a r k a r S C a n d K h a r u l U K 2 0 1 0 N e w N -s ub s t i -
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2 7 . C h e n Z , Y u X a n d S o n g Y 2 0 1 6 P a l l a d i u m
n a n o p a r t i c l e s u p p o r t e d o n m e s o p o r o u s p o l y b e n z i m -
i d a z o l e a s a h e t e r o g e n e o u s c a t a l y s t f o r S u z u k i c r o s s -
c o u p l i n g r e a c t i o n i n a q u e o u s m e d i a Ferroelectrics
494 2 0 0
7 . T h a t ha g ar B M B , B e c k e r s J a n d R o t h e n b e rg G 2 0 0 3
C o m bi n at o r i a l d e s i g n o f c o p p e r b a s e d m i x e d n a n o c lu s -
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L a w t o n T J , B a b e r A E , T i e r n e y H L , F l y t z a n i-
S t e p h an op ou l o s M a n d S y k e s E C H 2 0 1 2 I s o la t e d
m et a l a to m g e o m e t r i e s a s a s t r a t e g y f o r s e l e c t iv e
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9 . S u s t m a n n R , H o p p P a n d H o l l P 1 9 8 9 R e a c t io n s o f
o r g a n ic h al i d e s w i t h o l e fi n s u n d e r N i ( 0 ) - ca ta l y s i s .
F o r ma l a dd it i o n o f h y d r o c a r b o n s t o C C -d o u b l e b o n d s
Tetrahedron Lett. 30 6 8 9
1 0 . K e l k ar A A , H a n o k a T , K u b o t a Y a n d S u g i Y 1 9 9 4 T h e
v i n y l at i o n o f b r o mo b i p h e n y l s u s i n g h o m o g e n e o u s
n i ck e l c at al y s t s Catal. Lett. 29 6 9
1 1 . I y e r S , R a m es h C a n d R a m a n i A 1 9 9 7 N i ( 0 ) c a t a l y z e d
r e ac t i o ns o f a r y l a n d v i n y l h a l i d e s w i t h a l k e n e s a n d
a lk y n e s Tetrahedron Lett. 38 8 5 3 3
2 8 . W h it c o m b e N J , H i i K K a n d G i b s o n S E 2 00 1
A d v a n c e s i n t h e H e c k c h e m is t r y o f a r y l b r o m i d e s a nd
c h l o r id e s Tetrahedron 57 7 4 4 9
1 2 . I y e r S , R am e s h C , S a r k a r A a n d W a d g a o n k a r P P 1 9 9 7
T h e v i n y la t io n o f a r y l a n d v i n y l h a l i d e s c a t a l y z e d b y
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3 0 . L u P , T e r a n i s h i T, A s a k u r a K , M i y a k e M a n d T os h i m a N
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s t ab l e s u p p or te d n a n o - a l l o y s f o r t h e c a t a l y t i c h y d r o -
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