1. Julie Thoubboron
11 May 2015
Cumulative Research Report
Background
The goal of this research project was to synthesize and perform structural work on mixed
valence copper cyanide complexes with the hope of designing new homo-metallic coordination
polymers. Cyanide coordinates strongly to both Cu(I) and Cu(II) but will reduce Cu(II) unless
the Cu(II) is stabilized somehow. This can be done by coordination with bidentate or tridentate
amine Lewis bases. Procedurally, these syntheses were performed via air oxidation of solutions
containing Cu(I) complexed to cyanide in the presence of amine ligand. Another synthesis
technique that was used was partial reduction of the cyanide ion of solutions containing Cu(II)
ion and amine ligand. Slow evaporation of these mixtures over the course of several days was
performed with the goal of formation of crystalline products. These new compounds had both
infra-red spectra and crystal density calculations performed on them. The structure of the
compounds was then determined by single crystal X-ray diffraction data using a CAD4
diffractometer.
The first base I focused on was 3(diethylamino)propylamine, abbreviated as pn.
The first prep attempted on this base, used pn, NaCN, and CuSO4·5H2O in a 12.3:16.4:6.1 mmol
ratio dissolved in 50 mL DI producting a dark green-brown solution with a slight precipitate
present. On top of this, was layered drop-wise via pipette a solution contatining pn and
CuSO4·5H2O in a 6.15:2.05 mmol ratio, dissolved in 25 mL DI. This prep was later discarded.
The second prep attempted on this base used pn and CuSO4·5H2O in a 12.3:4.0 mmol ratio. This
was dissolved in 20mL DI. pn was then added with the hope of turning the solution dark blue.

2. This was continued until a total of 40.1mmol of base had been added. After a week, this mixture
became dark blue and concentrated, the precipitate dissolved. 20 mL DI were added to dilute the
sample which was then separated via pipette into two equal partitions.
The first of these partitions was combined with 50mg NaCN dissolved in 5mL DI,
producing no significant change. After 6 days, significant evaporation had occurred with a green
precipitate present in dark blue-green solution. No crystals were present. The same amount of
NaCN was added again with mixing. After 1 week, the prep has evaporated further, with green
solid in blue liquid present, so filtration was performed, separating a precipitate of solid forrest
green powder. This filtrate was later re-filtered, resulting in a blue filtrate with a light, mossy
green precipitate present that did not appear crystalline.
The second partition had a solution of 1mL NaCN, CuCN+
with 4mL DI layered onto it.
Immediately upon contact, a bright green precipitate was formed where the two solutions came
into contact. After 6 days, no crystals were present and no significant change had occurred.
Vacuum filtration was then performed, with a green powder precipitate recovered. After 1 week,
the filtrate had white crystalline material present, which was likely NaCN that came out of
solution.
The third prep attempted on this base used NaCN and CuCN in a 92.76:55.94 mmol ratio with
69.95 mmol pn dissolved in 20mL DI. After 1 week, this prep was a light yellow-green liquid,
with a green gelatinous substance suspended above the liquid. DI was added in 5mL increments
in attempt to dissolve the prep. After 10mL DI added, the solid present broke up, but the white
solid did not dissolve. 50% as much pn was added again (34.98mmol). This prep was then
discarded following H2O2 addition.

3. The fourth prep attempted on this base used CuSO4·5H2O and pn in a 4.0:16.13 mmol ratio
dissolved in 5mL DI. Initially, a light blue precipitate was present, but disappeared relatively
quickly upon stirring. An additional 3.85mmol of base was added via pipette, followed by
4.23mmol NaCN in 3mL DI. A green precipitate was formed immediately upon addition. This
prep was later discarded.
The fifth prep attempted on this base tried to utilize a 1:1 95% ethanol: DI solution to dissolve
the NaCN with the intention of slowing down the layering process. A 5mL solution was used to
dissolve 4.08mmol NaCN. The previous prep was then repeated using this NaCN solution. When
the NaCN solution was layered on via pipette, a reaction was immediately evident upon the two
solutions touching. A bright green crust was formed over the dense, deep blue pn solution. After
1 week, the solution appears green, with crust still present and no crystals present, so the solution
was discarded.
The sixth prep attempted on this base repeated the previous prep, except with half the amount of
CuSO4·5H2O. Immediately upon mixing, the solution became dark blue with solid present, which
disappeared upon further mixing. To the initial base mixture, 5mL DI was slowly pipetted on as
a top layer with the intention of creating a barrier layer to slow the mixing in of the NaCN
solution, which was added next. This prep was later discarded.
The seventh prep attempted on this base used CuCN and NaCN in a 2.8:4.6 mmol ratio dissolved
in 10mL DI, with 10.4mmol of pn. No immediate color change occurred and no precipitate
immediately formed. After 1 week, the prep had a green gelatinous upper layer over a yellow
liquid solid layer with no solid visibly present. The prep was stirred to reintegrate the solid and
place on a hot plate on low heat with mechanical stirring for 1.5 hours. After heating and stirring,
the solution was light yellow and viscous with no solid present.

4. The second base I focused on was N,N-diethyldiethylenetriamine, abbreviated as detdien.
The first prep attempted on this base used CuSO4·5H2O, detdien, and NaCN in a 1:3:2 mmol
ratio, dissolved in 15mL DI. The solution turned dark blue with no immediate precipitate
present. After 1 week, some small green crystals were present. They were filtered off via
decantation and the filtrate was left to sit. After 1 more week, the filtrate has some more
crystalline material present. The filtrate was then separated into two partitions.
The first partition was left as is. After 1 week, a significant amount of green, non-
crystalline material was present.
The second partition was placed in a hot water bath and heated without boiling, then
allowed to cool and left to sit. After 1 week, a significant amount of green crystalline material
was present, in greater quantities than had been seen previously in any other prep attempt.
The second prep attempted on this base used CuSO4·5H2O, detdien, and NaCN in a 1:4:2 mmol
ratio in an attempt to create more of the same crystals created by the previous prep. No solid was
immediately present in the solution. After 1 week, very few crystals were visible in the vial, so
the prep was heated in a hot water bath without boiling for approximately 30 minutes. After 1
more week, significant amount of dark black crystals were present. These were extracted and
transferred onto a slide for x-ray.
The third prep attempted on this base used CuSO4·5H2O, detdien, and NaCN in a 1:3:2 mmol
ratio. The solution was dark blue with no immediate precipitate present. After 1 week, a small
amount of dark crystalline material was present in a deep purple solution. Vacuum filtration was
performed, and the solid was found to be a mixture of the previously found green crystals and
black crystals. The filtrate was left to sit.

5. The fourth prep attempted on this base repeated the previous prep except with 150% as much
base. Upon mixing, the solution turned dark blue with no precipitate immediately present. After
1 week, there was still no solid material present and the prep was discarded.
The third base I focused on was N,N’-dimethylethanolamine, abbreviated as dm-oen.
The first prep attempted on this base used NaCN, CuCN, and dm-oen in a 38.46:23.22:21.22
mmol ratio in 12mL DI. Upon mixing, the solution turned light pink in color and was left to sit.
After 2 weeks, the prep turned a teal color with gelatinous, clear material present. The prep was
dissolved in 20mL water and 50% as much base was added. The solution turned a darker purple
color as a result. After 1 week, the prep returned to its gelatinous form, so 5mL of DI were added
in hopes of dissolving, but this was unsuccessful and the prep was discarded.
The second prep attempted on this base followed the same protocol as the previous attempt. The
resulting solution was a light brown color. After 1 week, the solution had turned a purple
translucent color with no crystals present. Some white precipitate was present, which was most
likely NaCN that had come out of solution. After 1 more week, the solution appeared to have a
very fine, light brown precipitate floating in a purple solution with no crystalline material
present. Vacuum filtration was then performed to remove the unwanted precipitate, and the
filtrate was saved. After 1 week, no solid appeared to be present and the prep was discarded.
The third prep attempted on this base repeated the same protocol as the previous attempt, except
with 50% more base. The mixture was a purple color with no precipitate immediately present.
After 1 month, the prep dried up so 20mL DI was added to dissolve the mixture. All solid went
back into solution except some white crystalline material which was most likely a salt in light
blue solution. This prep was eventually discarded.
The most successful base, detdien, produced black crystals which were further analyzed.

6. A density calculation was performed on one of the black crystals that resulted from the detdien
preps. A rough density indicated that the crystal sinks slowly in 1.5g/mL.
In order to perform the density calculation, the solutions 1,2,3-trichloropropane (1.387g/mL) and
1,2-dibromoethane (2.17g/mL) were used. The calculation was done three times, and an average
was taken.
First calculation:
Weight of 25mL volumetric flask: 18.9901g
Filled with 25mL DI: 43.8434g
Weight of 25mL DI: 43.8434g – 18.9901g = 24.853g
Density of DI water: (25.853g)/(25mL) = 0.994g/mL
Weight of 25mL volumetric flask: 18.9951g
Filled with 25mL density solution: 57.3175g
Weight of 25mL density solution: 57.3175g – 18.9951g = 38.3224g
Density of solution/crystal: (38.3224g)/(25mL) = 1.532g/mL
Second calculation:
Weight of 25mL volumetric flask: 18.989g
Filled with 25mL DI: 43.747g
Weight of 25mL DI: 43.747g – 18.989g = 24.758g
Density of DI water: (24.758g)/(25mL) = 0.990g/mL
Weight of 25mL volumetric flask: 18.994g
Filled with 25mL density solution: 57.370g
Weight of 25mL density solution: 57.370g – 18.994g = 38.376g
Density of solution/crystal: (38.376g)/(25mL) = 1.535g/mL

7. Third calculation:
Weight of 25mL volumetric flask: 18.9886g
Filled with 25mL DI: 43.6368g
Weight of 25mL DI: 43.6368g – 18.9886g = 24.648g
Density of DI water: (24.648g)/(25mL) = 0.986g/mL
Weight of 25mL volumetric flask: 19.0033g
Filled with 25mL density solution: 57.4265g
Weight of 25mL density solution: 57.4265g – 19.0033g = 38.4235g
Density of solution/crystal: (38.4235g)/(25mL) = 1.537g/mL
Corrections and Average:
Average weight of 25mL DI: (24.853g + 24.758g + 24.648g)/3 = 24.753g
Corrected first density: (38.3224g)/(24.753mL) = 1.548g/mL
Corrected second density: (38.3224g)/(24.753mL) = 1.550g/mL
Corrected third density: (38.4235g)/(24.753mL) = 1.552g/mL
Average density: (1.548g/mL + 1.550g/mL + 1.552g/mL)/3 = 1.550g/mL