Cobalt (III) Coordination Compounds

Synthesis Reactions

Quick Reminder about plagiarism

This is the BIG report this semester, so we dont take plagiarism lightly Why? 1. Unfair to others 2. In real life you could lose your job! If we find: page copied 25% off lab score page copied 50% off lab score 1 page copied 100% off lab score

The Cobalt Experience

Week 1: Synthesize a known compound, either J or Q. Begin researching and writing. Week 2: Synthesize an unknown compound. Keep researching and writing

S Q T J

D M W

The Cobalt Experience

Week 3: Complete two of four characterizations. Keep researching and writing. Week 4: Do the other two characterization tests. Keep researching and writing Week 5: Finish characterizations if you havent already. Week 6: Spring Break for non-Chem 205 students. Week 7: Turn in the report.

Cobalt Coordination Chemistry

This is going to be a four week synthesis and characterization lab. Basic idea we are going to make some Co(III) complexes:

Then, youll make another, unknown complex, in which the NH3 ligands, and the Cl- will be altered to e.g., F-, NO3-, SO42-, etc. Then well find the structure

 Cobalt coordination complexes are known since 1850s are important in history of inorganic chemistry, Crystal Field Theory (CFT), redox, isomerism etc.

Synopsis of Synthesis
All compounds created will have an octahedral arrangement of six ligands about Co3+. Known Compound Q [Co(NH3)6]Cl3 Known Compound J [Co(NH3)5Cl]Cl2 Unknown Compounds S, T, D, M, W [Co(NH3)xLy]Xz nH2O

Unknown Parameters
[Co(NH3)xLy]Xz nH2O x+y=6 x0 y1 n0

L = H2O, OH-, NO2-, NO3-, F-, Cl-, Br[NO2- = ONO- or NO2-]

X = NO3-, F-, Cl-, Br-

Isomers
Geometric
Cis vs. Trans

Facial (fac) vs. Meridional (mer)

Linkage
Nitrito vs. nitro

Characterization Tests
Molar mass Number of ammonia ligands Identity of non-ammonia ligands Charge of complex ion

But more on these in another lecture

Labile and Inert Compounds

What does this mean for Co?

Co(III) is inert, so we may have difficulty doing many inner sphere reactions with it So we use Co(II) which is kinetically labile Co(III) is really stable due to large crystal field stabilization energy (CFSE) associated with low spin d6 configuration. However, you can do reactions on some inner sphere ligands
Mn+ inner sphere outer sphere intervening medium

[Co(NH3)xLy]n+ (SO42-)n

Oxidation
Labile to Inert

d7

d6

Known Synthesis
Q and J: [Co(II)(H2O)6]Cl2 + NH4Cl + NH4OH [Co(II)(NH3)6]Cl2 + H2O2
(III) (III)

[Co(II)(NH3)6]Cl2

[Co(III(NH3)5(H2O)]Cl3
[Co(NH3)5OH]2+ [Co(NH3)5(H2O)]3+

J: [Co(III(NH3)5(H2O)]Cl3 + HCl

[Co(III)(NH3)5Cl]Cl2

Q: [Co(III(NH3)5(H2O)]Cl3 + C + HCl

[Co(III)(NH3)6]Cl3

(III)

C
[Co(II)(NH3)5(H2O)]2+ C+ C

NH3 [Co(II)(NH3)6]2+
e-

C+

[Co(III)(NH3)6]3+ C

Some Concerns
You are dealing with some pretty dangerous chemicals Unwanted reactions are a possibility. Dont do that. Watch your waste. You are working with others under the hood for extended periods of time.

Cover ALL Chemicals

Concentrated ammonia and concentrated HCl react in the air Concentrated ammonia and concentrated HCl are not fun to breathe. Even dry chemicals can have bad reactions when exposed to open air, and possible spills

Working in the Hood

Keep the sash down. Keep your heads out of the hood.

Important: Must use hood as indicated!!

SO2, SO3 choking gases, forms H2SO4 in lungs NO2 choking gas, forms HNO3 in lungs NaNO2 toxic Oxalic acid toxic (rhubarb leaves) Ethanol flammable, toxic Acetone flammable, toxic Work in hood as much as possible, use aspirators in lab Coats on racks Book bags well aware from hoods Take care with acids

Ammonium Fluoride
NH4F can form HF HF can etch glass HF can absorb through your skin HF can eat at your bones

Waste
Organic waste (acetone, ethanol) Acidic waste Basic waste Dont mix these!

Dropwise means dropwise

When the directions say dropwise, we mean dropwise When the directions say slowly, we mean slowly

30% H2O2
Hydrogen Peroxide in the store is 3% Avoid contact with the skin Do not allow H2O2 to contact unreacted solid on the inside of the flask. H2O2 is a great oxidizer and ethanol and acetone are reducing agents DO NOT MIX THESE

Filtration
B chner funnels Dont use too much water Dont scratch sintered glass filters Filtrate or solid?

Vacuum filtration using a Crucible

A glass sintered crucible. The Vacuum Filtration set-up you will be using in this experiment.

Care and Tips

Great care with acids and bases: H2SO4, HNO3, NaOH Keep coats, books, bags etc. well out of the way. Record EVERYTHING in your notebook Do calculations, and as much writing as you go Dont save it all for the end Take great care with acetone dont put it near the Bunsens! First lab runs long, but later labs shorter

Care and Tips

Label solutions well! (especially [Co(NCS)4]2- blue Co standard solution Use H2O2 very carefully, dont pour on compounds or sides of flasks it will decompose dilute 30% to 3% If you get black Co2O3 in synthesis, remove by filtration Pour carefully!!

Vs.

To-Do List
We will convert the Co complexes to [Co(NCS)4]2- which is bright blue, and from its absorbance we can determine %Co and molar mass by UV-Vis spectroscopy. Well also find the number of NH3 by removing NH3 with NaOH and titrating the NH3s Plus, well find the charge on the cation by using it to displace H+ from an Ion-Exchange resin column, and we will titrate to get the charge. This will give us a good chance of getting the total structure