Maricris Monica N.

Cabreros

 In 1893, at the age of 26, Alfred Werner "stepped

outside the box" and proposed his coordination theory that revolutionized the field of inorganic chemistry.

 Werner synthesized the green trans and violet cis

isomer of [Co(NH3)4Cl2]2+

Stereoisomers
Compounds having the same atom to atom bonding

but differ only in spatial arrangement of atoms or groups around central metal atom.

Structural Isomerism
A type of isomerism that arises due to different

arrangement of coordinating groups around the central metal atom in coordination sphere

Ionization Isomerism
exists in coordination compounds having the same

chemical composition but gives different ions if dissolved in a solution. For this kind of isomerism, an interchange of ligand between the coordination sphere of metal ion and ions inside the sphere occurs.

Hydration Isomerism
occurs when there is an interchange of water molecule

and another ligand between the first coordination sphere and the other ligand outside it. [Cr(H2O)4Cl2]Cl 2H2O-green; [Cr(H2O)5Cl]Cl2 H2O blue-green; and [Cr(H2O)6]Cl3-violet

Coordination Isomerism
isomerism which is observed in coordination

compounds having both cationic and anionic parts as coordination ions. In this category, isomers are formed if ligands between two metal centers are interchanged
[Co(NH3)6][Cr(Cn)6] and [Cr(NH3)6][Co(CN)6]

Linkage Isomers
isomerism takes place when the same ligand has two

possible coordination sites this means the ligand has two atoms which can donate electron pairs to metal ions these ligands are commonly called as ambidentate ligands

Ambidentate ligands
CN- (cyano) links to C NC- (isocyano) links to N OCN- (cyanato) links to O NCO- (isocyanato) links to N SCN- (thiocyanato) links to S NCS(isothiocyanato) links to N atoms

Nitrate Ion

two different resonance structures, each with the

negative charge on a different oxygen atom. binds through the lone pair of the central atom: nitrogen for the nitro form and oxygen for the nitrito form.

Goal
to synthesize the linkage isomers nitro- and nitrito- of

pentaamminecobalt(III) chloride understand the knowledge behind linkage isomerism to characterize the products using Infrared spectroscopy and their reactions in different conditions (presence/absence of light and heat).

 Nitrito and Nitro isomer

Preparation of [CoCl(NH3)5]Cl2
15 grams of ammonium carbonate in 250mL E. flask 75 mL water 40 mL concentrated ammonia 9.25 grams cobalt(II) chloride hexahydrate in 25 mL water Place in a 500 mL suction flask attached with a rubber stopper connected to an aerator Gently draw air for about two hours

In the preparation the Co cobalt chloride is the source of

ion ammonium carbonate is the source of carbonate (CO32-) and ammonia (NH3) ligands. The long aeration process was done to oxidize the metal Co2+ to Co3+ by reacting with the oxygen brought by the aeration process.

2+

 The following steps can be summarized in a reaction

equation written as follows

Co2+ + 4NH3 + HCO3- + 1/2O2

[Co(NH3)4CO3]+ + 1/2 H2O

Oxidation of the Co2+ to Co3 is done in aqueous medium

liberate the HCO3- from ammonium carbonate Co in pure aqueous medium is predominantly

controlled by oxidation Co2+ at ambient conditions, Eo = 1.81 + 0.06 log Co2+/Co3+ Co3+ has a extremely low solubility so it will only be observed in aqueous solutions with strong chelating molecule

Crystal Field Stabilization Energy

In the ligand field, d-orbitals are split and some of

them become lower in energy than before with respect to a spherical field known as the barycenter, where all five d-orbitals are degenerate. In an octahedral case, the t2g becomes lower in energy than the orbitals in the barycenter.

 If electrons occupy these orbitals, the metal ion is

more stable in the ligand field relative to the barycenter by an amount known as the CFSE.
CFSE= (6Dq x no. of e-s in eg) (4Dq x no. of e-s in t2g)

 CFSE= (6Dq x no. of e-s in eg) (4Dq x no. of e-s in

t2g)

 In the spectrochemical series, the value of CFSE

increases along the series so having water in the weak field stabilizes the Co2+ more since a more negative CFSE value indicates a more stable configuration.

transferred to a beaker

1.5 grams of ammonium chloride

was gently heated until crystals started to appear at the surface Concentrated HCl, until no further evolution of gas observed

 concentrated HCl was added dropwise to expel CO2

evident as evolution of gas. Also this makes the reaction forward to attain equilibrium, stated by the Le Chateliers principle
[Co(NH3)4CO3]+ + 2H3O+ [Co(NH3)4(H2O)2]3+

+ CO2 + H2O

 CO32- was just

replaced by water through ligand substitution reaction

Concentrated ammonia, until neutralized

5 mL more concentrated aqmmonia steam bath for 45 minutes

 concentrated NH3 was added to neutralize the mixture

and serve as the source of the NH3 ligand. The solution was heated to drive the reaction forward by evaporation of water through heating the mixture in a steam bath.
[Co(NH3)4(H2O)2]3+ + NH3

[Co(NH3)5(H2O)]3+ + H2O

40 mL concentrated HCl

Continued to heat for 30 minutes

Cooled to room temperature Cool in an ice bath until no more significant changes observed

 . Water ligands are displace due to addition on

concentrated HCl which contributed large amounts of reacting chloride ions and also combined with heating the mixture in steam bath which allowed the evaporation of water.
[Co(NH3)5(H2O)]3+ + 3Cl- [Co(NH3)5Cl]Cl2 + H2O

Filter
Residue Wash with min. amounts cold water and cold ethanol Air dry [CoCl(NH3)5]Cl2 Filtrate
Acid waste bin

overall reaction for the synthesis of pentaamminechlorocobalt(III) chloride

Co2+ + 5 NH3 + HCO3- + 1/2O2 + 2H3O+ + 3Cl- [Co(NH3)5Cl]Cl2 + 7/2H2O + CO2

Synthesis of [CoCl(NH3)5]Cl2
Reagent/Action taken ammonium carbonate addition of water addition of concentrated ammonia addition of cobalt chloride solution aeration of solution addition of ammonium chloride addition of concentrated HCl addition of concentrated ammonia heating Observation white crystals clear colorless solution clear colorless solution dark purple dark purple with distinct ammonia odor dark purple evolution of gas violet mixture formation of light violet layer at the bottom evolution of gas, formation of light violet precipitate at the bottom and surface purple mixture purple solid

addition of concentrated HCl

filtrate residue

Preparationgrams 5 of [Co(NH3)5ONO]Cl2
[CoCl(NH3)5]Cl2
1.5 mL concentrated ammonia in 80 mL water Gently heat

Filter
Residue
Solid wast ebin

Filtrate
Cool in ice bath

Filtrate
titrated with 2M HCl until the solution is neutral 5 g. NaNO2 5 mL 6M HCl Stand for one hour

Filter
Residue
Wash with 2mL cold water and 25mL cold ethanol, dry [Co(NH3)5ONO] Cl2

Filtrate
Acid waste bin

 Reaction with water makes the reaction forward

[Co(NH3)5Cl]Cl2 + H2O [Co(NH3)5 H2O]3+ + 3Cl-

 Filtrate was then treated with HCl to provide chloride

ions and NaNO2 to provide the nitrite ion. Theoretically :red-orange in color In the experiment: light-yellow brown precipitate.
[Co(NH3)5 H2O]3+ + Cl- + NO2- H2O +

[Co(NH3)5ONO]Cl2 + H2O

 Due to the doubtful bulk product formed, the

synthesis of [Co(NH3)5NO2]Cl2 was not made

Preparation of [Co(NH3)5ONO]Cl2
Reagent/Action taken [Co(NH3)5Cl]Cl2 addition of concentrated ammonia addition of water heating residue filtrate cooling of filtrate titration with 2M HCl addition of NaNO2 addition of 6M HCl ice bath filtrate residue after washing

Observation purple solid purple mixture with purple solids purple mixture with purple solids brownish purple mixture light purple solids brownish purple brown mixture brown solution (neutralized) formation of few bubbles; brown mixture formation of bubbles on the surface of the brown mixture formation of precipitate at the bottom of the brown mixture brown liquid mixture brown solids light yellow-brown solid

Oxygen-nitrosation
reactive species is actually not [Co(NH3)5 H2O]3+ but

the conjugate base of the complex, [Co(NH3)5(OH)]2+. This reacts with N2O3 to form the nitrito isomer and nitrous acid, HNO2.

 In here, the oxygen bonded to the Cobalt ion in the

nitrito complex was originally from the water ligand, and not from the nitrite ion ligand.

 Theoretically if the nitro isomer was to be prepared,

after the [Co(NH3)5ONO]Cl2 crystals were filtered and dried, they will be dissolved in hot water. A few drops of aqueous ammonia will be added then a red orange solution will appeare. While cooling the mixture, concentrated HCl will be added and a yellow-brown product is expected as the nitro-isomer.

yellow-brown solid already appeared skipped the formation of the nitrito forwarded and
product

 Formation of the nitro product is more favourable

since the product is more resonance stabilized.

Co-N bond is stronger than Co-O bond because

oxygen is more electronegative than nitrogen making the bond with cobalt less strong

Characterization
Observations Nitrito

Niitro

exposure to UV light light pink to light pink yellow brown to light pink to yellow brown heating to >100o C aging in dark light pink to yellow brown light pink to yellow brown yellow brown to yellow brown yellow brown to yellow brown

 The nitrito isomer is the kinetically labile product

since it forms immediately due to a low activation energy. Activation energy is defined as the energy that must be overcome in order for a chemical reaction to occur.

 Heating the nitrito isomer increases the kinetic energy

of molecules and therefore more nitrito- molecules have enough energy to overcome the activation E barrier to form the thermodynamically stable nitro isomer

 . upon standing, isomerization of nitrito to nitro

isomer can also occur since there is enough time for the equilibrium to be reached. Heating simply speeds up the rate for reaching equilibrium of a reaction.

 Exposing the nitro isomer on UV light resulted to the

formation of nitrito isomer. This is because nitrito isomer requires lower energy to form and is kinetically favored. Therefore, the nitro isomer is considered as the more stable isomer at room conditions, upon aging and heating.

 - nitropentaamminenitritocobalt(III) chloride, [Co(NH3)5NO2]Cl2 --- nitritopentaamminenitritocobalt(III) chloride, [Co(NH3)5ONO]Cl2,

freshly prepared . nitritopentaamminenitritocobalt(III) chloride, [Co(NH3)5ONO]Cl2, aged

IR spectroscopy
Nitro Isomer (Fresh Sample) Mode of Wavenumber Vibration (cm-1) NO2 845 scissoring, NH3 rocking H-N-H 1600 asymmetric scissoring NO2 1430 asymmetric stretching NH3 rocking 850
NO2 symmetric stretching, HN-H symmetric scissoring 1300

Nitrito Isomer Nitrito Isomer (Fresh Sample) (Aged Sample) Mode of Wavenumber Mode of Wavenumber Vibration (cm-1) Vibration (cm-1) ONO 850 NO2 scissoring, 845 scissoring, NH3 rocking NH3 rocking H-N-H 1316 H-N-H 1600 symmetric asymmetric scissoring scissoring H-N-H 1618 NO2 1430 asymmetric asymmetric scissoring stretching N-O stretching 1060 NH3 rocking 850 1460 NO2 symmetric stretching, HN-H symmetric scissoring

 1600 cm-1, 1316 cm-1 and 850 cm-1 and the said bands

can be assigned as degenerate deformation vibrations, symmetric deformation vibrations and rocking vibrations of NH3 ligands

 The vibrations of the NH3 ligands of the nitrito isomer

were observed at 1618 cm-1, 1316 cm-1, and 1600 cm-1

the vibrations of the NH3 ligands of the nitro isomer

were found at 850 cm-1and 1600 cm-1

 The spectrum of the aged nitrito isomer is almost

identical to the spectrum of the nitro isomer. This proves that as the nitrito isomer aged it becomes the nitro isomer.

 On aging nitrito ligand, the spectra showed bands

which can be assigned to the nitro ligand. Therefore, the strong bands that decrease in intensity can be assigned to the nitrito isomer which shows the rearrangement of the nitrito isomer to the more stable nitro isomer.

Recommendation
It is recommended that a much less time be allowed in

heating the nitrito mixture since this may have resulted to the conversion of the nitrito isomer to the nitro form. Also a comparison between concentrated and dilute system can be made.

Summary and Conclusion

Linkage isomers arise when ligands bind to a central

metal ion through either one of the two possible donor atoms.
linkage isomers [Co(NH3)5ONO]Cl2 and

[Co(NH3)5NO2]Cl2 were synthesized using the intermediate [Co(NH3)5Cl]Cl2.

 The nitro isomer is more stable upon heating and

ageing than the nitrito isomer. Also the nitrito isomer is converted to nitro isomer when exposed to heat or upon standing for an extended period of time.

 Upon exposure to UV light, the nitro isomer turned

into the nitrito isomer.

The nitrito isomer is kinetically favored while the nitro

isomer is the one which is thermodynamically stable.