Linkage Isomers: Synthesis and Characterization of
[Co(NH 3 ) 5 ONO]Cl 2 and [Co(NH 3 ) 5 NO 2 ]Cl 2
Divalent cobalt is more stable than trivalent cobalt for simple salts of cobalt, with only a few salts of Co(III) known (e.g. CoF 3 ). Formation of a coordination complex stabilizes a higher oxidation state as evidenced by a number of octahedrally coordinated complexes. In this experiment, you will prepare two linkage isomer compounds, [Co(NH 3 ) 5 ONO]Cl 2 and [Co(NH 3 ) 5 NO 2 ]Cl 2 .
1) The synthesis of [Co(NH 3 ) 4 CO 3 ]NO 3 involves the following unbalanced equation,
Co(NO 3 ) 2 + NH 3 (aq) + (NH 4 ) 2 CO 3 + H 2 O 2 [Co(NH 3 ) 4 CO 3 ]NO 3 + NH 4 NO 3 + H 2 O
Cobalt nitrate [Co(NO 3 ) 2 ]
is deliquescent (tends to absorb atmospheric water vapor and become liquid). Upon exposure to atmospheric moisture, cobalt nitrate has the formula Co(NO 3 ) 2 6H 2 O.
Co(II) complexes react very rapidly by ligand exchange, thus a possible first step in the reaction:
Co(OH 2 ) 6 2+
+ 4NH 3 (aq) + CO 3 2-
Co(NH 3 ) 4 CO 3 + 6H 2 O
Which could then be oxidized by addition of H 2 O 2 to form [Co(NH 3 ) 4 CO 3 ] + .
2) One synthesis scheme of [Co(NH 3 ) 5 Cl]Cl 2 involves the following equations,
[Co(NH 3 ) 5 (OH 2 )] 3+ + 3HCl [Co(NH 3 ) 5 Cl]Cl 2 (s) + H 2 O + 3H +
[Adapted From: Tanaka, J. and Suib, S.L.. Experimental Methods in Inorganic Chemistry; Prentice-Hall: 1999 and Jolly, W.L. The Synthesis and Characterization of Inorganic Compounds Prentice-Hal: 1970.] 2 3) Synthesis of [Co(NH 3 ) 5 ONO]Cl 2 and [Co(NH 3 ) 5 NO 2 ]Cl 2 involves the following:
[Co(NH 3 ) 5 Cl] 2+ + H 2 O [Co(NH 3 ) 5 H 2 O] 3+ + Cl -
[Co(NH 3 ) 5 H 2 O] 3+ + NO 2 - [Co(NH 3 ) 5 ONO] 2+ + H 2 O
Make a solution of 5.0 g ammonium chloride NH 4 Cl
in 30 mL of concentrated aqueous ammonia in a 250 mL Erlenmeyer flask. While stirring with magnetic stirbar, slowly add 10 g of cobalt(II) chloride hexahydrate. While continuously stirring, slowly add 8 mL of a 30% H 2 O 2
solution (CAUTION: H 2 O 2 is a strong oxidizing agent that can cause severe burns. Use gloves! Wash affected areas immediately with water!). When evidence of further reaction has ceased, slowly add 30 mL of concentrated HCl. Heat the solution using a hot plate in a fume hood. Maintain a temperature of about 85C for about 20 minutes. Do not allow the solution to boil. Cool the solution slightly and then place in an ice water bath. Isolate the crystalline product by suction filtration. Wash the product with a small amount of ice-cold water. The total volume of the wash should not exceed 15 mL. Wash with 15 mL of cold 6M HCl. Allow the product to dry on the filter paper and then weigh the product to determine the approximate yield. Discard the filtrate wash solution in the in the appropriate cobalt waste containers in the fume hood.
Heat a solution (do not boil) of 8 mL of concentrated aqueous ammonia in 80 mL of water. While heating and stirring, add 5.0 g of dry [Co(NH 3 ) 5 Cl]Cl 2
or 6.0 g wet [Co(NH 3 ) 5 Cl]Cl 2 . Continue heating, below boiling point, and stirring until the product dissolves. This may take 15 minutes or more. If you observe the presence of a dark brown to black precipitate of cobalt oxide, filter it off. Cool the solution to about 10 C. Add 2 M HCl slowly while keeping the solution cold until it is neutral as determined by litmus or pH paper. Add 5.0 g of sodium nitrite followed by 5 mL of 6 M HCl. Cool the solution in an ice bath for approximately an hour, then filter the precipitated salmon pink crystals of [Co(NH 3 ) 5 ONO]Cl 2 . Wash with 20 mL of icewater then 20 mL of 95% 3 ethanol. Allow it to dry on the lab bench for approximately one hour before collecting the IR and UV-Vis spectrum.
The product [Co(NH 3 ) 5 ONO]Cl 2 is not stable and will isomerize to [Co(NH 3 ) 5 NO 2 ]Cl 2 . Ensure you have sufficient time in the laboratory session to collect the IR spectrum of the product on the same day as the synthesis.
Pentaamminenitrocobalt(III) chloride, [Co(NH 3 ) 5 NO 2 ]Cl 2
The product [Co(NH 3 ) 5 ONO]Cl 2 will isomerize to [Co(NH 3 ) 5 NO 2 ]Cl 2 at room temperature given sufficient time. The isomerization may also be facilitated by heating. It is possible to use the [Co(NH 3 ) 5 ONO]Cl 2 product before it is completely dry. Bring 20 mL of H 2 O to a boil and add a few drops of NH 4 OH. Turn off heat and allow cooling for 4 minutes after boiling has ceased. Add 2.0 g of [Co(NH 3 ) 5 ONO]Cl 2 to the solution. As this solution cools to room temperature, add 20 mL of concentrated HCl. After cooling from solution, [Co(NH 3 ) 5 NO 2 ]Cl 2 will precipitate from solution. Filter the product from solution and wash with small portions of a total of 10 mL 95% ethanol. Allow to dry under vacuum for several minutes until dry and collect the IR spectrum and the UV-Vis spectrum.
Ensure UV-visible and IR spectra have been collected for each of the three products, [Co(NH 3 ) 5 Cl]Cl 2 , [Co(NH 3 ) 5 ONO]Cl 2 , and [Co(NH 3 ) 5 NO 2 ]Cl 2 .