Synthesis of Bis(triphenylphosphine) copper(I) nitrate

Aim :- 

Synthesis of Bis(triphenylphosphine) copper(I) nitrate.

Appratus :- 

1. Beaker
2. reflux condensor 
3. volumetric and round bottom flask 
4. stirrer
5. Burner
6. water bath 
7. thermometer 

Chemical Requirements:-  

1. Copper(II)nitratetrihydrate, 
2. triphenyl phosphine
3. methanol
4. diethylether.

Theory:- 

The chemical formula of Bis(triphenylphosphine) copper(I) nitrate is [Cu[P(C6H5)3] 2(NO3)].The action of triphenylphosphine on copper(II) nitrate trihydrate in methanol mixtures gives rise to the complex CuNO3 (PPh3)2 . X-ray crystallographic study of CuNO3 (PPh3)2 has shown it to contain tetrahedrally coordinated copper(I) and a bidentate nitrato group . In this complex the P--Cu—P angle was found to be quite large and there seems to be little reason why a third triphenylphosphine ligand could not be coordinated if the nitrato group is bidentate. The P--Cu—P bond angle is 131.1o The nitrate group is bidentate with N-O bond distance is 1.21Ao. Triphenylphosphine ligand is a pi acceptor ligand so it stabilizes the Cu(I) metal ion. The complex bis(triphenylphosphine) could be converted into the complex tris(triphenylphosphine) by treating it with the ligand in warm ethanol.    

2 Cu(NO3)2. 3H2O +5P(C6H5)3 → 2[Cu[P(C6H5)3].2(NO3)] + OP(C6H5)3 +2HNO3 + 5H2O       

Procedure : - 

• Take 4.9 g of Cu(NO3)2. 3H2O into a solution of triphenylphosphine (21 g, 0.08 mole) in 200 mL of hot methanol.Copper nitrate dissolve immediately to form a clear solution.
• The special precautions are not required for the exclusion of air throughout this synthesis.But near the end of the addition a heavy white precipitate forms.
• After addition of all the Cu(NO3)2. 3H2O the reaction suspension is heated at reflux for 5 minutes and then cooled to ambient temperature.
• The white precipitate is filtered, washed well with ethanol and diethyl ether, and air dried to give [Cu[P(C6H5)3 ]2(NO3)].
• This crude powder is recrystallized from hot methanol to give white needles when the filtered solution is cooled temperature.
• Then we will check the melting point point of crude and crystallised complex. Also check the IR of the complex.       

     

Characterization of  Bis(triphenylphosphine)copper (I) nitrate :- 

• The melting point of the complex is 230℃.
• The nitrato group in this complex is bidentate since its IR spectrum shows a seperation of 200 cm -1 . It shows two strong peaks at 1280 and 1480 cm-1.  
• Triphenylphosphine has a peak at 3050 cm-1.

Properties of Bis(triphenylphosphine)copper (I) nitrate :- 

• This complex is white in colour .
• This is readily soluble in chloroform, dichloromethane, acetonitrile, and N,N-dimethylformamide at room temperature and is moderately soluble in hot methanol, ethanol, benzene, and tetrahydrofuran.
• Unlike a number of organophosphine complexes of copper(I) halides, [Cu[P(C6H5)3 ]2(NO3)] exhibits no fluorescence.
• Weak coordination of the nitrate anion is indicated by the solid-state infrared spectrum of the complex. 
• The facile dissociation of the nitrate ligand in this complex and other analogous copper(I) nitrate complexes makes them useful reagents for the introduction of other anionic ligands.

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Uses :-  

Bis(triphenylphosphine)copper(I) Nitrate is one of the numerous organometallic compounds which are useful reagents ,catalysts, and precursor materials with applications in thin film deposition , industrial chemistry ,LED manufacturing.