Mitchell Zembower

SCH 348 01

Research Plan

10 October 2022

Synthetic Ligand:

a) Rationale

Nickel and copper carbene complexes have both been shown to dehydrogenate ammonia borane.

The use of copper carbene complexes for dehydrogenation will be explored due to its ability to

easily change the R groups on the carbene. Ethyl bromide, bromobutane, and bromopentane will

be used to make the different imidazoles that will coordinate to the copper iodide. Copper iodide

is used because it has been shown to readily coordinate to imidazole complexes.

b & c) Reaction Scheme and Tables

Figure 1: Reaction Scheme of 1-butylimidazole1

Table 1: Reaction Table of 1-butylimidazole

imidazole 1- Potassium acetonitrile 1-

 bromobutane hydroxide butylimidazole

Molecular 68.08 g/mol 137.020 56.11 g/mol 41.05 g/mol 124.18 g/mol

Weight g/mol

Mass 0.018 g 0.037 g 0.030 g 1.3 g 0.033 g

mmol 0.27 mmol 0.27 mmol 0.54 31.7 mmol 0.27 mmol

Equivalence 1 eq 1 eq 2 eq 117 eq 1 eq

Volume 0.29 mL 1.6 mL

Density 1.27 g/mL 0.786 g/mL

Figure 2: Reaction Scheme of 1,3-dibutylimidazolium bromide1

Table 2: Reaction Table of 1,3-dibutylimidazolium bromide

1- 1-bromobutane acetonitrile 1,3-

butylimidazole dibutylimidazole

bromide
 Molecular 124.18 g/mol 137.020 g/mol 41.05 g/mol 261.202

Weight

Mass 0.033 g 0.041 g 0.57 g 0.0705 g

mmol 0.27 mmol 0.30 mmol 13.9 mmol 0.27 mmol

Equivalence 1 eq 1.1 eq 52 eq 1 eq

Volume 0.046 mL 0.73 mL

Density 1.27 g/mL 0.786 g/mL

Figure 3: Reaction of copper (I) 1,3-dibutylimidazolium complex2

Table 3: Reaction Table of copper (I) 1,3-dibutylimidazolium complex

1,3- Copper (I) Potassium acetone Cu(I) NHC

dibutylimidazole iodide carbonate

bromide
 Molecular 261.2 g/mol 190.45 138.20 g/mol 58.08 g/mol 371.75

Weight g/mol g/mol

Mass 0.0705 g 0.051 g 0.075 g 0.784 g 0.1 g

mmol 0.27 mmol 0.27 mmol 0.54 mmol 13.5 mmol 0.27 mmol

Equivalence 1 eq 1 eq 2 eq 50 eq 1 eq

Volume 1 mL

Density 0.784 g/mL

d) Experimental Procedure

A) Procedure for the synthesis of 1-butylimidazole1

1. Imidazole (0.018 g, 0.27 mmol) was dissolved in acetonitrile (1.6 mL) and placed

in a flask. Potassium hydroxide (0.030 g, 0.54 mmol) was added to the flask and

the mixture was heated to 60 oC while stirring.

2. 1-bromobutane (0.037 g, 0.27 mmol, 0.29 mL) was added dropwise to the

mixture.

3. The mixture was stirred for 24 hours at 60 oC.

4. The mixture was cooled to room temp and rotary evaporated.

5. The product was purified by column chromatography of silica gel with ethyl

acetate/methanol (25:1) as eluent.

B) Procedure for the synthesis of 1,3-dibutylimidazolium bromide1

1. 1-butylimidazole (0.033 g, 0.27 mmol) was dissolved in acetonitrile (0.73 mL) and

heated to 70 oC while stirring.

 2. 1-bromobutane (0.041 g, 0.30 mmol, 0.046 mL) was added dropwise to the

mixture.

3. The mixture was stirred for 96 hours at 70 oC.

4. After stirring, remaining oil was cooled to room temp and was washed with ethyl

acetate (3 x 0.6 mL) and with diethyl ether (3 x 0.2 mL)

C) Procedure for copper (I) 1,3-dibutylimidazolium complex2

1. 1,3-dibutylimidazole bromide (0.0705 g, 0.27 mmol) was placed in a vial with

copper (I) iodide (0.051 g, 0.27 mmol), potassium carbonate (0.075 g, 0.54

mmol), and acetone (1 mL).

2. This mixture was stirred at 60 oC for 24 hours.

3. After 24 hours, the solution was filtered through silica and washed with

dichloromethane (3 x 1 mL).

4. The solvent was then concentrated under vacuum and pentane (3 mL) was added

to precipitate the desired product.

5. The product was then vacuum-filtered and washed with pentane (3 x 1 mL).

e) Hazards

Imidazole – burns the eye and skin and harmful if absorbed through the skin. Harmful if

swallowed and can cause gastrointestinal tract burns

1-bromobutane – causes eye, skin and digestive tract irritation. Can be harmful if absorbed

through the skin or inhaled.

Potassium hydroxide - highly corrosive and can burn the skin and eyes. Can also irritate lungs,

nose, and throat. It may also cause skin allergies.

Acetonitrile – easily ignited and can cause eye, skin, and respiratory tract irritation

1-butylimidazole – causes skin irritation and serious eye damage. Fatal if inhaled.

1,3-dibutylimidazole bromide – N/A (1,1-dimethylimidazole bromide can cause eye and skin

irritation)

Copper (I) iodide – can cause skin irritation and serious eye irritation. Harmful if swallowed and

can cause respiratory irritation.

Potassium carbonate – causes serious eye irritation and skin irritation. Harmful if swallowed or

inhaled.

Acetone – exposure to skin drying and crackling of the skin with redness. Can also irritate the

eyes, nose, and throat.

Cu(I) NHC – N/A

f) Stability

No inert conditions are required; this product is air stable.

g) References

1) Rola, P. K.; Zajac, A.; Szpecht, A.; Kowal, D.; Cyninska, J.; Smiglak, M.; Komorowska.

Interaction of electron beam with ionic liquids and its application for micropatterning. Eur.

Polym. J. 2021, 156, 110615.

2) Santoro, O.; Collado, A.; Slawin, A. M. Z.; Nolan, S. P.; Cazin, C. S. J. A general synthetic

route to [Cu(X)(NHC)] (NHC = N-heterocyclic carbene, X = Cl, Br, I) complexes. Chem.

Commun. 2013, 49, 10483-10485.

Purchased Ligand:

a) Rationale

Fe(acac)3 has been shown to dehydrogenate many different secondary alcohols. This complex is

more economically and environmentally friendly compared to precious metals that are typical for

dehydrogenations. Cu(acac)2 and Ni(acac)2 complexes have been reported in literature, but not

for dehydrogenation uses. Fe, Cu, and Ni acac complexes will be explored to see their effect on

the dehydrogenation of ammonia borane. Fe,Cu, and Ni acac complexes are cheap, available,

and relatively easy to make.

b) Reaction Scheme

Figure 2: Reaction Scheme of copper (II) acetylacetonate3

c) Reaction Table
 Copper (II) Acetylacetone Potassium Water Copper (II)

acetate hydroxide acetylacetonate

monohydrate

Molecular 199.65 g/mol 100.13 g/mol 56.11 g/mol 18.02 261.764 g/mol

Weight g/mol

Mass 0.080 g 0.087 g *added until 2.39 g 0.10 g

solution had

a pH 8

mmol 0.40 mmol 0.87 mmol 138 mmol 0.40 mmol

Equivalence 1 eq 2.2 eq 345 eq 1 eq

Volume 0.0886 mL 2.4 mL

Density 0.980 g/mL 0.997

g/mL

d) Experimental Procedure

Synthesis of copper (II) acetylacetonate3

1. Copper (II) acetate monohydrate (0.08 g, 0.40 mmol) was dissolved in 2.4 mL of water in

a beaker by heating at 60 oC for 15 mins while stirring.

2. The solution was cooled and then 20% aqueous solution of KOH was slowly added with

constant stirring. The KOH solution was added until a pH of 8.

3. The metal hydroxide was washed free of alkali by repeated washing with water by

decantation. This solution was then filtered using filter paper and a funnel and washed

with cold water.

 4. The precipitate was transferred to a beaker and distilled acetylacetone (0.0886 mL) was

added to the precipitate and was mixed with a glass stirring rod.

5. This reaction was let undisturbed for 30 mins and then placed in an ice-water bath for 15

mins.

6. The compound was filtered through a funnel and dried in vacuo over fused CaCl2.

e) Hazards

Acetylacetone – flammable, causes eye, skin, and respiratory tract irritation

Copper (II) acetate monohydrate – harmful if swallowed, inhaled, or absorbed through the skin

Potassium hydroxide – highly corrosive and can burn the skin and eyes. Can also irritate lungs,

nose, and throat. It may also cause skin allergies.

Copper (II) acetylacetonate – causes eye, skin, and respiratory irritation

f) Stability

No inert conditions are required; this product is air stable.

g) References

3) Kanti, C. M.; Kumar, D. S.; Sankar, D. S.; Upasana, B.; Manoranjan, C. B.; Kantam, M. L.

Process for making metal acetylacetones. U.S. Patent US 2004127690A1, July, 1, 2004.