Preparation of a N-heterocyclic carbene complex of copper(I) thiocyanate

Preparation of a N-heterocyclic
carbene complex of copper(I)
thiocyanate
Student name: Zihan.Yin
Lab Group: 1
Date: 23/10/2024

When completing this pro-forma, remember to make use of the supporting information on
the CH315 Myplace page:

The 3rd Year Laboratory Manual

Guides on: experimental protocols, yield calculations and spectral analysis
Documents detailing experimental techniques

In order to assign the NMR spectra correctly, you will need to label the structures provided.
To do this, install ChemDraw on your computer and double click each structure and you will
open ChemDraw with the structure in. Make your changes in ChemDraw, then close
ChemDraw and the changes will be saved in this MSWord template.

Also, you may ask for help, or discuss sections of this pro-forma by emailing the Inorganic
course organiser: christopher.dodds@strath.ac.uk

Please remember to convert your completed pro-forma to pdf before uploading to the
relevant Myplace assignment.

Mark break-down by section:

Products /12

Experimental Protocols /3

% Yield Calculations /3

ATR-IR /2

NMR Spectroscopy Interpretation /8

Theory /2

Total /30

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 Preparation of a N-heterocyclic carbene complex of copper(I) thiocyanate

Reaction schemes and yield calculations

Synthesis of glyoxal-bis(2,6-dimethylphenyl)diimine

Complete the following table, using the values recorded in your laboratory note book and
the information in the experimental instructions.

Table 1. Quantities of chemicals used in the synthesis of glyoxal-bis(2,6-

dimethylphenyl)diimine

compound molar mass / g mol-1 mass / g moles / mmol

2,6-dimethylaniline
121.18 4.92 40.6
(d=0.984 g/mL)
40% (w/v) glyoxal solution 58.04 1.20 20.7

Which is the limiting reagent?

2,6-dimethylaniline
Calculate your yield of glyoxal-bis(2,6-dimethylphenyl)diimine, showing your working below:
Ratio of stoichiometry of 2,6-dimethylaniline:glyoxal-bis(2,6-dimethylphenyl)diimine =2:1
%yield=2 x actual moles of product/theoretical moles of product x100%
=2 x[mass of the glyoxal-bis(2,6-dimethylphenyl)diimine/molar mass of the glyoxal-bis(2,6-
dimethylphenyl)diimine]/[mass of the 2,6-dimethylaniline /molar mass of the 2,6-
dimethylaniline]x100%
=2 x(3.77 g/264 g/mol)/(4.92 g/121.18 g/mol)x100%
=70.35%

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 Preparation of a N-heterocyclic carbene complex of copper(I) thiocyanate

Experimental
Write a concise, scientific account of your experimental procedure for the synthesis of
glyoxal-bis(2,6-dimethylphenyl)diimine.
5 drops of formic acid was added to the mixture of 2,6-dimethylaniline (5
mL, 40.60 mmol), 40% glyoxal solution (3 mL,20.7 mmol) and isopropanol (30
mL).The mixture was stirred. The product was isolated by filtration, washed
with cold isopropanol (~20 mL)and dried by suction(overnight), giving
glyoxal-bis(2,6-dimethylphenyl)diimine (3.77 g,14.28 mmol,70.35 %) as
yellow crystalline solids.

Characterisation by ATR-IR
Assign the IR spectrum of your product. Report all strong/isolated absorption wavenumber
values and indicate those that are a result of key functional groups.

ATR-IR, � / cm–1 (Glyoxal-bis(2,6-dimethylphenyl)diimine): 3025~2733, 1621 (C=N), 1474

(C=C, phenyl),1188,823,761.

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 Preparation of a N-heterocyclic carbene complex of copper(I) thiocyanate

ATR-IR Spectrum
Insert an image of your recorded ATR-IR spectrum for glyoxal-bis(2,6-
dimethylphenyl)diimine on this page.

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 Preparation of a N-heterocyclic carbene complex of copper(I) thiocyanate

Synthesis of 1,3-bis(2,6-dimethylphenyl)imidazolium chloride

Complete the following table, using the values recorded in your laboratory note book and
the information in the experimental instructions.

Table 2. Quantities of chemicals used in the synthesis of 1,3-bis(2,6-

dimethylphenyl)imidazolium chloride

compound molar mass / g mol-1 mass / g moles / mmol

glyoxal-bis(2,6-
264 2.5 9.47
dimethylphenyl)diimine
paraformaldehyde 30.03 0.28 9.32
chlorotrimethylsilane
108.64 1.0 9.46
(d=0.856 g/mL)

Which is the limiting reagent?

Paraformaldehyde
Calculate your yield of 1,3-bis(2,6-dimethylphenyl)imidazolium chloride, showing your
working below:
Ratio of stoichiometry of paraformaldehyde:1,3-bis(2,6-dimethylphenyl)imidazolium
chloride=1:1
%yield=actual moles of product/theoretical moles of product x100%
=[mass of the 1,3-bis(2,6-dimethylphenyl)imidazolium chloride/molar mass of the 1,3-
bis(2,6-dimethylphenyl)imidazolium chloride]/[mass of the paraformaldehyde/molar mass
of the paraformaldehyde] x100%
=(0.457 g/300.5 g/mol)/(0.28 g/30.03 g/mol) x 100%
=16.31%

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 Preparation of a N-heterocyclic carbene complex of copper(I) thiocyanate

Experimental
Write a concise, scientific account of your experimental procedure for the synthesis of 1,3-
bis(2,6-dimethylphenyl)imidazolium chloride.

Glyoxal-bis(2,6-dimethylphenyl)diimine (2.5 g,9.47 mmol), paraformaldehyde

(0.28 g,9.32 mmol) and ethyl acetate (80 mL) was added and the mixture was
stirred and heated(100 °C) to reflux. A solution of chlorotrimethylsilane
(1.2 mL, 9.46 mmol) in ethyl acetate (2 mL) was added dropwise into the
refluxing mixture,forming a colorless solution.The mixture was refluxed
(1.5 hours).The mixture was cooled (10 °C),giving a beige coloured
product.The product was isolated by filtration and washed with acetone (20
mL) and dried by suction,giving 1,3-bis(2,6- dimethylphenyl)imidazolium
chloride (0.457 g,1.65 mmol,16.31 %) as beige crystalline solids.

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 Preparation of a N-heterocyclic carbene complex of copper(I) thiocyanate

Synthesis of (1,3-bis(2,6-dimethylphenyl)imidazol-2-ylidene)copper(I) thiocyanate

Complete the following table, using the values recorded in your laboratory note book and
the information in the experimental instructions.

Table 3. Quantities of chemicals used in the synthesis of (1,3-bis(2,6-

dimethylphenyl)imidazol-2-ylidene)copper(I) thiocyanate

compound molar mass / g mol-1 mass / g moles / mmol

1,3-bis(2,6-
dimethylphenyl)imidazolium 292.5 0.75 2.56
chloride
copper(I) thiocyanate 122.64 0.33 2.69

Which is the limiting reagent?

1,3-bis(2,6-dimethylphenyl)imidazolium chloride
Calculate your yield of (1,3-bis(2,6-dimethylphenyl)imidazol-2-ylidene)copper(I) thiocyanate,
showing your working below:
Ratio of stoichiometry of 1,3-bis(2,6-dimethylphenyl)imidazolium chloride:(1,3-bis(2,6-
dimethylphenyl)imidazol-2-ylidene)copper(I) thiocyanate
=1:1
%yield=actual moles of product/theoretical moles of product x100%
=[mass of the (1,3-bis(2,6-dimethylphenyl)imidazol-2-ylidene)copper(I) thiocyanate
/molar mass of the (1,3-bis(2,6-dimethylphenyl)imidazol-2-ylidene)copper(I)
thiocyanate]/[mass of the 1,3-bis(2,6-dimethylphenyl)imidazolium chloride/molar mass of
1,3-bis(2,6-dimethylphenyl)imidazolium chloride] x100%
=(0.066 g/398 g/mol)/(0.75 g/292.5 g/mol) x100%
=6.47%

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 Preparation of a N-heterocyclic carbene complex of copper(I) thiocyanate

Experimental
Write a concise, scientific account of your experimental procedure for the synthesis of
(1,3-bis(2,6-dimethylphenyl)imidazol-2-ylidene)copper(I) thiocyanate.

1,3-bis(2,6-dimethylphenyl)imidazolium chloride (0.75 g,2.4 mmol), copper(I)

thiocyanate (0.33 g,2.69 mmol) and anhydrous potassium carbonate (3.32
g,24.06 mmol) was added and suspended in acetone (40 mL).The mixture was
heated,stirred and refluxed (1 hour). The resulting hot mixture was
isolated by filtration and dried in vacuo.The crystalline solid was
isolated by filtration and dried in a vacuo,giving (1,3-bis(2,6-
dimethylphenyl)imidazol-2-ylidene)copper(I) thiocyanate (0.066 g,0.17
mmol,6.47 %)as light pink crystalline.

State the melting point of your product

m.p. / oC: 232.2 oC

Characterisation by ATR-IR
Assign the IR spectrum of your product. Report all strong/isolated absorption wavenumber
values and indicate those that are a result of key functional groups.

ATR-IR, � / cm–1 ((1,3-bis(2,6-dimethylphenyl)imidazol-2-ylidene)copper(I) thiocyanate):

3152~2923, 2092, 1472 (C=N), 1230, 949, 785, 739, 700.

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 Preparation of a N-heterocyclic carbene complex of copper(I) thiocyanate

ATR-IR Spectrum
Insert an image of your recorded ATR-IR spectrum for (1,3-bis(2,6-dimethylphenyl)imidazol-
2-ylidene)copper(I) thiocyanate on this page.

NMR Spectroscopy Interpretation

Interpret the 1H NMR spectra for products B & C and the 13C NMR spectra for product C. All
the NMR spectra are available on the Myplace site for CH315. (The Heteronuclear Single
Quantum Correlation (HSQC) spectrum is also available to help with your 13C assignments.
In essence HSQC is a proton detected experiment that shows directly attached carbons.
Therefore, quaternary carbons cannot be identified by HSQC. However, for this experiment
by using the 1D 13C spectrum and the 2D HSQC spectrum you should be able to assign all
the carbon atoms.

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 Preparation of a N-heterocyclic carbene complex of copper(I) thiocyanate

1
H NMR (CDCl3, 400 MHz): δ 10.99 (1H,s,A),7.68(2H,s,B),7.31(2H,t,J=7.6
Hz,C),7.17(4H,d,J=7.6 Hz,D),2.18(12H,s,E).

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 Preparation of a N-heterocyclic carbene complex of copper(I) thiocyanate

1
H NMR (CDCl3, 400 MHz): δ 7.32(2H,t,J=6.0 Hz,A),7.21(4H,d,J=6.4
Hz,B),7.09(2H,s,C),2.11(12H,s,D).

C NMR (CDCl3, 100 MHz): δ

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δ178.47(a),137.45(b),134.98(c),133.86(d),129.92(e),129.04(f),122.46(g),17.88(h)

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 Preparation of a N-heterocyclic carbene complex of copper(I) thiocyanate

Theory

For the reaction sequence shown below identify the products A and B.

A:CuCl

B:

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