Suzuki Coupling:

Aqueous and Anhydrous Synthesis of Ferrocene-Capped Thiophene

Fe S Fe

Bill Mitchell 2003-04

Introduction
Polythiophene
p-type semiconducting organic polymer Tuneable electronic properties

S
n

Polythiophene

Introduction
Applications
Photovoltaics (solar cells)
Cheaper Higher voltage Activated by visible light Tuning will improve efficiency
* S
n

Transistors, light emitting diodes

Cheaper More efficient Smaller

Introduction
Problem
No cyclic voltammetry
Polymerization

Ferrocene
End-cap for thiophene Electrochemically active
Fe
Ferrocene

Introduction
Short chain vs. long chain
Solubility Yield Accuracy
S Fe n Fe
Fe S S n S Fe

n= 1, 2, 3

n= 3, 4

Short chain

Long chain

Procedure 1:
Aqueous 2,5-Diferrocenyl-Thiophene

Suzuki Coupling
Aqueous
Highly contaminated Low yield
OH B 2 Fe OH Br S Br PdCl2(d ppf) S Fe Fe

+ 2 NaOH(a q)
In dimetho xyethane re flux 120 h r.

Side Reaction

B Fe

OH OH Fe

HOH

B(OH)3

Anhydrous Coupling
Organic soluble
Boronic ester Less contamination Higher yield
O B O Fe

1-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-ferrocene

Procedure 2:
1-(4,4,5,5-Tetramethyl-1,3,2-Dioxabolan-2-yl)-Ferrocene (Boronic Ester)

OH B OH Fe HO

O B O HO in pen tane Fe

HOH

PPh3 Fe S X PPh3 Pd

PPh3 PPh3

Procedure 3:
Anhydrous 2,5-DiferrocenylThiophene
Br S X Fe X = Br,

PPh3

PPh3 Pd 2 PPh3

Fe PPh3 S PPh3 Pd

X Br PPh3 PPh3 S Pd

X O

Br

Fe K3PO4 + Fe

In dioxane Reflux 96-120 hr.

KBr

K2PO4

O B O

Results
Solvent Catalyst 5-10 mol% dependant on scale NiBr2(PPh3)2 PdCl2(dppf) NiBr2(PPh3)2 NiCl2(dppe) NiCl2(dppe) PdCl2(dppf) (PPh3)4Pd(0) open bottle (PPh3)4Pd(0) fresh bottle NiCl2(dppe) NiCl2(dppe) PdCl2(dppf) (PPh3)4Pd(0) fresh bottle (PPh3)4Pd(0) fresh bottle Excess Ligand equivalent on catalyst 1 PPh3 none none 2 dppe 2 dppe none 2 PPh3 2 PPh3 2 dppe 2 dppe none 2 PPh3 2 PPh3 Reducing Agent equivalent on catalyst fully reduced 2 n-BuLi 2 n-BuLi 2 n-BuLi .5 n-BuLi none .5 n-BuLi none none .25 added after 20 hr. .375 n-BuLi .375 n-BuLi none none Base 3 equiavalents on boronic ester potassium t-butoxide potassium t-butoxide potassium t-butoxide potassuim t-butoxide potassium t-butoxide potassium carbonate potassium carbonate potassium carbonate potassium phosphate potassium phosphate potassium phosphate potassium phosphate potassium phosphate Time Yield (starting materials) THF dioxane dioxane dioxane dioxane dioxane dioxane dioxane dioxane dioxane dioxane dioxane dioxane 72 hrs 48 hrs 72 hrs 44 hrs 18 hrs 48 hrs 24 hrs 120 hrs 44 hrs 120 hrs 44 hrs 96 hrs 96 hrs 0% (~100%) 0% (~0%) 0% (~0%) 0% (~0%) 0% (~0%) 0% (~100%) 0% (~100%) 2.5% (N/A) 0% (90%) 0% (~100%) 0% (~95%) trace (42%) 5% (69%)

Results:
Aqueous 2,5-Diferrocenyl-Thiophene
1H

NMR spectrum

250 MHz

Fe S Fe

Conclusion
Synthesize Ferrocene-Capped Thiophene
Aqueous method Chromatography eluent less polar
50:50 hexane:dichloromethane 70:30 hexane:dichloromethane

Further Research
Make Derivatives
Electron donating and withdrawing Electrochemical characterization
Variable temperature

Applications
Photovoltaics Transistors

Suzuki Coupling:
Aqueous and Anhydrous Synthesis of Ferrocene-Capped Thiophene
Fe S Fe

Bill Mitchell 2003-04

Chemical Shift

observed shift (Hz )*10 6 6 250 *10 (Hz )