A

 Step  Towards  Ar.ficial  Photosynthesis:  

 Renewable  Amines  for  CO2  Reduc.on  
Edward  J.  Holland,  Chris  Stanley,  Robert  D.  Richardson,  Barry  K.  Carpenter  
With   insight   gained   from   mechanis.c   studies   of   photochemical   CO2   reduc.on   we   have   developed   a   renewable   amine   capable   of   ac.ng   as   a   source   of   both  
electrons  and  H  atoms  in  such  reac.ons.  We  have  shown  that  this  amine  is  capable  of  reducing  CO2  and  that  it  gives  a  single  alkene  product;  further  we  have  
shown  this  product  can  be  hydrogenated  back    to  the  original  amine.  This  system  is  proposed  as  a  prototype  ar.ficial  photosynthesis  of  formic  acid.  We  hope  
further   works   can   increase   the   total   efficiency   of   the   system   and   remove   dependence   on   UV   light.   The   work   presented   here   is   largely   focused   on   the   synthesis  
of  the  first  genera.on  amine  and  progress  towards  second  genera.on  amines.  

1   2   Photochemical  CO2  Reduc)on  

Introduc)on  
H2
It   is   widely   recognised   that   the   earth   is   undergoing   climate   change  
and   there   are   significant   nega.ve   effects   associated   with   this.   The   Alkene Amine   radical   ca.ons   are   common  
role   of   atmospheric   CO2   concentra.on   in   global   warming   is   widely   R3N
H H intermediates  in  CO2  reduc.ons,  and  
accepted.  It  seems  we  must  seek  to  lower  CO2  concentra.ons  in  order  
hv
PTP* computa.onal   studies   in   our   group  
R3N
to   move   towards   sustainable   living.   This   is   possible   in   two   ways:   h a v e   p r e d i c t e d   t h a t   t h e s e  
reducing   CO2   emissions   and   sequestering   carbon   capture   CO2.   An   PTP
intermediates   are   capable   of   giving  
PTP
ar.ficial   photosynthesis   scheme   could   achieve   both   these   goals   if   it   alkene  products  aUer  dona.on  of  a  H  
produced   a   fuel   that   could   be   used   to   meet   current   energy   demands.   atom   to   a   CO2   radical   anion.   Further  
If   photochemical   CO2   reduc.on   and   photochemical   water   spliSng   experimental  work  has  developed  an  
could   be   coupled   then   an   ar.ficial   photosynthe.c   system   could   be   amine   that   successfully   realises   the  
envisioned.   Both   these   reac.ons   are   known   in   many   forms;   it   is   our   CO2 CO2 predicted   chemistry.   This   is   the   first  
aim   to   develop   methodology   to   allow   the   coupling   of   the   two   H H report  of  a  renewable  amine  for  CO2  
reac.ons   by   a   third   reac.on.   We   have   iden.fied   a   common   r e d u c . o n ,   a s   s h o w n   b e l o w.  
HCOOH
intermediate   in   photochemical   CO2   reduc.ons   that   is   an   aTrac.ve   O O
H
target  to  design  a  reagent  capable  of  coupling  the  two  reac.ons.  We   PTP, hv > 290nm, CO2
H
have   managed   to   develop   a   prototype   reagent   and   show   its   use   in   H d7-DMF or CD3CN

photochemical  CO2  reduc.on.                           H H

N
H
N

PTP  –  para-­‐Terphenyl   H COOH

3   4   Synthesis  of  a  2nd  Genera)on  Amine  

Synthesis  of  a  Renewable  Amine  
O F3C O
O
1) AgBF4, DCM
t-Butyl
Ot-Butyl A  second  genera.on  of  amines  
H

Cl
H
N N N perbenzoate TFA
O based   on   pyridine   has   been  
Cl
CuBr
Benzene designed.   The   norbornane  
MgSO4, Cyclohexane 2) NaOH
H2O, MeOH N core   is   accessible   from  
Boc norbornadiene   through     7  
1) H2, Pd/C, EtOH
LiAlH4
THF oxonorborane.   Addi.on   of  
2) NaBH4, EtOH
O O nucelophiles   to   this   ketone  
OH
O O OH have   proved   some   what  
H2, Pd/C
PCC, Silica gel, troublesome.   Nonetheless  
EtOH DCM
products   for   preliminary  
LiAlH4, THF
N N
Me2SO4
KH N studies  have  been  synthesised.  
DMF
Boc Boc
2-Li-Pyr
THF
2-Li-DMAP, THF
Unfortunately   the   pyridyl  
N analogue  appears  to  be  unable  
To   promote   the   desired   chemistry   over   compe.ng   side   reac.ons   a   to   transfer   its   electron   to   PTP.  
distant   H   atom   must   be   held   close   to   the   nitrogen   centre.   It   is   also   It   is   believed   the   DMAP  
advantageous  to  deac.vate  α-­‐H  atoms.  This  amine  has  been  designed   N
OH
N
OH
analogue   will   be   more  
with  these  constraints  in  mind.  The  key  step  in  the  synthe.c  scheme   successful  once  its  synthesis  is  
is  a  [4,3]  cycloaddi.on  reac.on  which  builds  the  tricyclic  core.     achieved.            

6  
5  
Re(bipy)(CO)3Cl  Photocatalysts   Conclusions  
To   show   wide   applicability   of   our   amine   •   Designed  and  synthesised  a  renewable  amine  for  CO2  reduc.on  
Cl
in   CO2   reduc.ons   we   must   inves.gate   •   No  requirement  for  sacrificial  electron  donors  in  CO2  reduc.on  
N CO the   use   of   organometallic   photo-­‐ •   Coupled  photochemical  CO2  reduc.on  and  water  spliSng  reac.ons  
Re catalysts.   We   start   our   inves.ga.on   •   Developed  prototype  ar.ficial  photosynthesis  of  formic  acid  
N CO
CO with   Re(bipy)(CO)3Cl.   Preliminary   •   Preliminary  results  indicate  wider  applicability  of  our  amine  
results   include   a   reduc.on   in   •   Second  genera.on  amines  in  development  
phosphorescence   life.me   with   Acknowledgements    
increasing   amine   concentra.on,  
We   wish   to   thank   everybody   involved   in   the   project;   especially   the  
detec.on   of   reduc.on   product   (CO)   by  
George  group  in  NoSngham  and  the  POC  centre  Cardiff.  We  also  wish  
GC-­‐TCD;   and   produc.on   of   alkene  
to   thank   those   who   have   funded   our   work:   Leverhumle   Trust,   EPSRC  
detected   by   NMR   studies.   All   these  
and  HEFCW.        
results   indicate   that   our   amine   is  
capable   of   reducing   CO2   with   a   Re(bipy)
References  
(CO)3Cl   photocatalyst,   however   these   B.  K.  Carpenter  et  al,  JACS.  2008,  130,  3169-­‐3180  
results   are   all   preliminary   and   we   seek   B.  K.  Carpenter  et  al,  Nature  Chem.  2011,  3,  301-­‐303  
B.  K.  Carpenter,  J.  Phys.  Chem.  A  2007,  111,  3719-­‐3726  
to   further   quan.fy   these   results.   We   F.  Williams  et  al,  Chem.  Eur.  J.  2004,  10,  5524-­‐5534  
BoTom:  Photochemical  sample  Top:  Photochemical  sample  spiked  
with  authen.c  alkene  
must   also   extend   the   work   to   more   E.  Fujita  et  al,  Acc.  Chem.  Res.  2009,  42,  1983-­‐1994    
photocatalysts.