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Q5.15 (iii):
Discuss the nature of bonding on the basis of valence bond theory: ([Co(C_{2}O_{4})_{3}]^{3-})
Solution :
Step 1: Determining the Oxidation State of the Central Metal Ion
To analyze the bonding, we first identify the oxidation state of the Cobalt ($Co$) ion in the complex $[Co(C_2O_4)_3]^{3-}$.
- The oxalate ion ($C_2O_4^{2-}$) carries a charge of $-2$.
- Let $x$ be the oxidation state of $Co$.
- The equation for the charge balance is: $x + 3(-2) = -3$
- $x - 6 = -3 \implies x = +3$.
[Per IUPAC nomenclature and charge conservation principles]. Thus, Cobalt is in the $Co^{3+}$ state.
Step 2: Electronic Configuration of $Co$ and $Co^{3+}$
- Atomic number of $Co = 27$. Ground state configuration: $[Ar] 3d^7 4s^2$.
- For $Co^{3+}$, three electrons are removed (two from $4s$, one from $3d$): $[Ar] 3d^6$.
Step 3: Crystal Field Considerations and Pairing
The oxalate ion ($C_2O_4^{2-}$) acts as a bidentate ligand. While it is often considered a weak-field ligand in the spectrochemical series, in the presence of $Co^{3+}$ (a high-charge metal ion), it induces pairing of the $d$-electrons to form a low-spin complex [Ref: Valence Bond Theory (VBT) postulate regarding pairing energy vs. crystal field splitting energy].
| Orbital Set | Configuration |
|---|---|
| $3d$ | $\boxed{\uparrow\downarrow} \boxed{\uparrow\downarrow} \boxed{\uparrow\downarrow} \boxed{\phantom{\uparrow}} \boxed{\phantom{\uparrow}}$ |
| $4s$ | $\boxed{\phantom{\uparrow\downarrow}}$ |
| $4p$ | $\boxed{\phantom{\uparrow\downarrow}} \boxed{\phantom{\uparrow\downarrow}} \boxed{\phantom{\uparrow\downarrow}}$ |
Step 4: Hybridization and Geometry
The complex requires six vacant orbitals to accommodate the six lone pairs donated by the three bidentate oxalate ligands. To achieve this, the two empty $3d$ orbitals, one $4s$ orbital, and three $4p$ orbitals hybridize to form six equivalent $d^2sp^3$ hybrid orbitals.
- Hybridization: $d^2sp^3$ (Inner orbital complex).
- Geometry: Octahedral.
- Magnetic Property: Since all electrons are paired, the complex is diamagnetic ($\mu = 0$ B.M.).
Step 5: Summary of Bonding Nature
- Hybridization: $d^2sp^3$.
- Geometry: Octahedral.
- Magnetic Behavior: Diamagnetic (all electrons paired).
- Spin state: Low-spin complex.
Final Solution: The complex $[Co(C_2O_4)_3]^{3-}$ exhibits $d^2sp^3$ hybridization, resulting in an octahedral geometry and diamagnetic behavior due to the pairing of electrons in the $3d$ orbitals.
More Questions from Class 12 Chemistry Coordination Compounds Exercises
- Q5.1: Explain the bonding in coordination compounds in terms of Wernerโs postulates.
- Q5.1: Explain the bonding in coordination compounds in terms of Wernerโs postulates.
- Q5.10 (i): Draw the structures of optical isomers of: ([Cr(C_{2}O_{4})_{3}]^{3-})
- Q5.10 (ii): Draw the structures of optical isomers of: ([PtCl_{2}(en)_{2}]^{2+})
- Q5.10 (iii): Draw the structures of optical isomers of: ([Cr(NH_{3})_{2}Cl_{2}(en)]^{+})
- Q5.10(i): Draw the structures of optical isomers of: \([Cr(C_{2}O_{4})_{3}]^{3-}\)
- Q5.10(ii): Draw the structures of optical isomers of: \([PtCl_{2}(en)_{2}]^{2+}\)
- Q5.10(iii): Draw the structures of optical isomers of: \([Cr(NH_{3})_{2}Cl_{2}(en)]^{+}\)
- Q5.11 (i): Draw all the isomers (geometrical and optical) of: ([CoCl_{2}(en)_{2}]^{+})
- Q5.11 (ii): Draw all the isomers (geometrical and optical) of: ([Co(NH_{3})Cl(en)_{2}]^{2+})
- Q5.11 (iii): Draw all the isomers (geometrical and optical) of: ([Co(NH_{3})_{2}Cl_{2}(en)]^{+})
- Q5.11(i): Draw all the isomers (geometrical and optical) of: \([CoCl_{2}(en)_{2}]^{+}\)
- Q5.11(ii): Draw all the isomers (geometrical and optical) of: \([Co(NH_{3})Cl(en)_{2}]^{2+}\)
- Q5.11(iii): Draw all the isomers (geometrical and optical) of: \([Co(NH_{3})_{2}Cl_{2}(en)]^{+}\)
- Q5.12: Write all the geometrical isomers of \([Pt(NH_{3})(Br)(Cl)(py)]\) and how many of these will exhibit optical isomers?
- Q5.12: Write all the geometrical isomers of ([Pt(NH_{3})(Br)(Cl)(py)]) and how many of these will exhibit optical isomers?
- Q5.13: Aqueous copper sulphate solution (blue in colour) gives: (i) a green precipitate with aqueous potassium fluoride and (ii) a bright green solution with aqueous potassium chloride. Explain these experimental results.
- Q5.13: Aqueous copper sulphate solution (blue in colour) gives: (i) a green precipitate with aqueous potassium fluoride and (ii) a bright green solution with aqueous potassium chloride. Explain these experimental results.
- Q5.14: What is the coordination entity formed when excess of aqueous \(KCN\) is added to an aqueous solution of copper sulphate? Why is it that no precipitate of copper sulphide is obtained when \(H_{2}S(g)\) is passed through this solution?
- Q5.14: What is the coordination entity formed when excess of aqueous KCN is added to an aqueous solution of copper sulphate? Why is it that no precipitate of copper sulphide is obtained when ((H_{2}S(g))) is passed through this solution?
- Q5.15 (i): Discuss the nature of bonding on the basis of valence bond theory: ([Fe(CN)_{6}]^{4-})
- Q5.15 (ii): Discuss the nature of bonding on the basis of valence bond theory: ([FeF_{6}]^{3-})
- Q5.15 (iv): Discuss the nature of bonding on the basis of valence bond theory: ([CoF_{6}]^{3-})
- Q5.15(i): Discuss the nature of bonding in the following coordination entities on the basis of valence bond theory: \([Fe(CN)_{6}]^{4-}\)
- Q5.15(ii): Discuss the nature of bonding in the following coordination entities on the basis of valence bond theory: \([FeF_{6}]^{3-}\)
- Q5.15(iii): Discuss the nature of bonding in the following coordination entities on the basis of valence bond theory: \([Co(C_{2}O_{4})_{3}]^{3-}\)
- Q5.15(iv): Discuss the nature of bonding in the following coordination entities on the basis of valence bond theory: \([CoF_{6}]^{3-}\)
- Q5.16: Draw figure to show the splitting of d orbitals in an octahedral crystal field.
- Q5.16: Draw figure to show the splitting of d orbitals in an octahedral crystal field.
- Q5.17: What is spectrochemical series? Explain the difference between a weak field ligand and a strong field ligand.
- Q5.17: What is spectrochemical series? Explain the difference between a weak field ligand and a strong field ligand.
- Q5.18: What is crystal field splitting energy? How does the magnitude of \(\Delta_{o}\) decide the actual configuration of d orbitals in a coordination entity?
- Q5.18: What is crystal field splitting energy? How does the magnitude of (\Delta_{o}) decide the actual configuration of d orbitals in a coordination entity?
- Q5.19: \([Cr(NH_{3})_{6}]^{3+}\) is paramagnetic while \([Ni(CN)_{4}]^{2-}\) is diamagnetic. Explain why?
- Q5.19: ([Cr(NH_{3})_{6}]^{3+}) is paramagnetic while ([Ni(CN)_{4}]^{2-}) is diamagnetic. Explain why?
- Q5.2: \(FeSO_{4}\) solution mixed with \((NH_{4})_{2}SO_{4}\) solution in 1:1 molar ratio gives the test of \(Fe^{2+}\) ion but \(CuSO_{4}\) solution mixed with aqueous ammonia in 1:4 molar ratio does not give the test of \(Cu^{2+}\) ion. Explain why?
- Q5.2: ((FeSO_{4})) solution mixed with ((NH_{4})_{2}SO_{4}) solution in 1:1 molar ratio gives the test of ((Fe^{2+})) ion but ((CuSO_{4})) solution mixed with aqueous ammonia in 1:4 molar ratio does not give the test of ((Cu^{2+})) ion. Explain why?
- Q5.20: A solution of \([Ni(H_{2}O)_{6}]^{2+}\) is green but a solution of \([Ni(CN)_{4}]^{2-}\) is colourless. Explain.
- Q5.20: A solution of ([Ni(H_{2}O)_{6}]^{2+}) is green but a solution of ([Ni(CN)_{4}]^{2-}) is colourless. Explain.
- Q5.21: \([Fe(CN)_{6}]^{4-}\) and \([Fe(H_{2}O)_{6}]^{2+}\) are of different colours in dilute solutions. Why?
- Q5.21: ([Fe(CN)_{6}]^{4-}) and ([Fe(H_{2}O)_{6}]^{2+}) are of different colours in dilute solutions. Why?
- Q5.22: Discuss the nature of bonding in metal carbonyls.
- Q5.22: Discuss the nature of bonding in metal carbonyls.
- Q5.23 (i): Give the oxidation state, d orbital occupation and coordination number of the central metal ion: (K_{3}[Co(C_{2}O_{4})_{3}])
- Q5.23 (ii): Give the oxidation state, d orbital occupation and coordination number of the central metal ion: (cis-[CrCl_{2}(en)_{2}]Cl)
- Q5.23 (iii): Give the oxidation state, d orbital occupation and coordination number of the central metal ion: ((NH_{4})_{2}[CoF_{4}])
- Q5.23 (iv): Give the oxidation state, d orbital occupation and coordination number of the central metal ion: ([Mn(H_{2}O)_{6}]SO_{4})
- Q5.23(i): Give the oxidation state, d orbital occupation and coordination number of the central metal ion in the following complexes: \(K_{3}[Co(C_{2}O_{4})_{3}]\)
- Q5.23(ii): Give the oxidation state, d orbital occupation and coordination number of the central metal ion in the following complexes: cis-\([CrCl_{2}(en)_{2}]Cl\)
- Q5.23(iii): Give the oxidation state, d orbital occupation and coordination number of the central metal ion in the following complexes: \((NH_{4})_{2}[CoF_{4}]\)
- Q5.23(iv): Give the oxidation state, d orbital occupation and coordination number of the central metal ion in the following complexes: \([Mn(H_{2}O)_{6}]SO_{4}\)
- Q5.24 (i): Write down the IUPAC name for the complex and indicate the oxidation state, electronic configuration and coordination number. Also give stereochemistry and magnetic moment of the complex: (K[Cr(H_{2}O)_{2}(C_{2}O_{4})_{2}].3H_{2}O)
- Q5.24 (ii): Write down the IUPAC name for the complex and indicate the oxidation state, electronic configuration and coordination number. Also give stereochemistry and magnetic moment of the complex: ([Co(NH_{3})_{5}Cl]Cl_{2})
- Q5.24 (iii): Write down the IUPAC name for the complex and indicate the oxidation state, electronic configuration and coordination number. Also give stereochemistry and magnetic moment of the complex: ([CrCl_{3}(py)_{3}])
- Q5.24 (iv): Write down the IUPAC name for the complex and indicate the oxidation state, electronic configuration and coordination number. Also give stereochemistry and magnetic moment of the complex: (Cs[FeCl_{4}])
- Q5.24 (v): Write down the IUPAC name for the complex and indicate the oxidation state, electronic configuration and coordination number. Also give stereochemistry and magnetic moment of the complex: (K_{4}[Mn(CN)_{6}])
- Q5.24(i): Write down the IUPAC name for each of the following complexes and indicate the oxidation state, electronic configuration and coordination number. Also give stereochemistry and magnetic moment of the complex: \(K[Cr(H_{2}O)_{2}(C_{2}O_{4})_{2}].3H_{2}O\)
- Q5.24(ii): Write down the IUPAC name for each of the following complexes and indicate the oxidation state, electronic configuration and coordination number. Also give stereochemistry and magnetic moment of the complex: \([Co(NH_{3})_{5}Cl]Cl_{2}\)
- Q5.24(iii): Write down the IUPAC name for each of the following complexes and indicate the oxidation state, electronic configuration and coordination number. Also give stereochemistry and magnetic moment of the complex: \([CrCl_{3}(py)_{3}]\)
- Q5.24(iv): Write down the IUPAC name for each of the following complexes and indicate the oxidation state, electronic configuration and coordination number. Also give stereochemistry and magnetic moment of the complex: \(Cs[FeCl_{4}]\)
- Q5.24(v): Write down the IUPAC name for each of the following complexes and indicate the oxidation state, electronic configuration and coordination number. Also give stereochemistry and magnetic moment of the complex: \(K_{4}[Mn(CN)_{6}]\)
- Q5.25: Explain the violet colour of the complex \([Ti(H_{2}O)_{6}]^{3+}\) on the basis of crystal field theory.
- Q5.25: Explain the violet colour of the complex ([Ti(H_{2}O)_{6}]^{3+}) on the basis of crystal field theory.
- Q5.26: What is meant by the chelate effect? Give an example.
- Q5.26: What is meant by the chelate effect? Give an example.
- Q5.27: Discuss briefly giving an example in each case the role of coordination compounds in: (i) biological systems (iii) analytical chemistry (ii) medicinal chemistry and (iv) extraction/metallurgy of metals.
- Q5.27(i): Discuss briefly giving an example in each case the role of coordination compounds in: biological systems
- Q5.27(ii): Discuss briefly giving an example in each case the role of coordination compounds in: medicinal chemistry
- Q5.27(iii): Discuss briefly giving an example in each case the role of coordination compounds in: analytical chemistry
- Q5.27(iv): Discuss briefly giving an example in each case the role of coordination compounds in: extraction/metallurgy of metals.
- Q5.28: How many ions are produced from the complex \(Co(NH_{3})_{6}Cl_{2}\) in solution?
- Q5.28: How many ions are produced from the complex (Co(NH_{3})_{6}Cl_{2}) in solution?
- Q5.29: Amongst the following ions which one has the highest magnetic moment value?
- Q5.29: Amongst the following ions which one has the highest magnetic moment value?
- Q5.3: Explain with two examples each of the following: coordination entity, ligand, coordination number, coordination polyhedron, homoleptic and heteroleptic.
- Q5.3: Explain with two examples each of the following: coordination entity, ligand, coordination number, coordination polyhedron, homoleptic and heteroleptic.
- Q5.30: Amongst the following, the most stable complex is
- Q5.30: Amongst the following, the most stable complex is
- Q5.31: What will be the correct order for the wavelengths of absorption in the visible region for the following: \([Ni(NO_{2})_{6}]^{4-}\), \([Ni(NH_{3})_{6}]^{2+}\), \([Ni(H_{2}O)_{6}]^{2+}\)?
- Q5.31: What will be the correct order for the wavelengths of absorption in the visible region for the following: ([Ni(NO_{2})_{6}]^{4-}), ([Ni(NH_{3})_{6}]^{2+}), ([Ni(H_{2}O)_{6}]^{2+})?
- Q5.4: What is meant by unidentate, didentate and ambidentate ligands? Give two examples for each.
- Q5.4: What is meant by unidentate, didentate and ambidentate ligands? Give two examples for each.
- Q5.5 (i): Specify the oxidation numbers of the metals: ([Co(H_{2}O)(CN)(en)_{2}]^{2+})
- Q5.5 (ii): Specify the oxidation numbers of the metals: ([CoBr_{2}(en)_{2}]^{+})
- Q5.5 (iii): Specify the oxidation numbers of the metals: ([PtCl_{4}]^{2-})
- Q5.5 (iv): Specify the oxidation numbers of the metals: (K_{3}[Fe(CN)_{6}])
- Q5.5 (v): Specify the oxidation numbers of the metals: ([Cr(NH_{3})_{3}Cl_{3}])
- Q5.5(i): Specify the oxidation numbers of the metals in the following coordination entities: \([Co(H_{2}O)(CN)(en)_{2}]^{2+}\)
- Q5.5(ii): Specify the oxidation numbers of the metals in the following coordination entities: \([CoBr_{2}(en)_{2}]^{+}\)
- Q5.5(iii): Specify the oxidation numbers of the metals in the following coordination entities: \([PtCl_{4}]^{2-}\)
- Q5.5(iv): Specify the oxidation numbers of the metals in the following coordination entities: \(K_{3}[Fe(CN)_{6}]\)
- Q5.5(v): Specify the oxidation numbers of the metals in the following coordination entities: \([Cr(NH_{3})_{3}Cl_{3}]\)
- Q5.6 (i): Using IUPAC norms write the formulas: Tetrahydroxidozincate(II)
- Q5.6 (ii): Using IUPAC norms write the formulas: Potassium tetrachloridopalladate(II)
- Q5.6 (iii): Using IUPAC norms write the formulas: Diamminedichloridoplatinum(II)
- Q5.6 (iv): Using IUPAC norms write the formulas: Potassium tetracyanidonickelate(II)
- Q5.6 (ix): Using IUPAC norms write the formulas: Tetrabromidocuprate(II)
- Q5.6 (v): Using IUPAC norms write the formulas: Pentaamminenitrito-O-cobalt(III)
- Q5.6 (vi): Using IUPAC norms write the formulas: Hexaamminecobalt(III) sulphate
- Q5.6 (vii): Using IUPAC norms write the formulas: Potassium tri(oxalato)chromate(III)
- Q5.6 (viii): Using IUPAC norms write the formulas: Hexaammineplatinum(IV)
- Q5.6 (x): Using IUPAC norms write the formulas: Pentaamminenitrito-N-cobalt(III)
- Q5.6(i): Using IUPAC norms write the formulas for the following: Tetrahydroxidozincate(II)
- Q5.6(ii): Using IUPAC norms write the formulas for the following: Potassium tetrachloridopalladate(II)
- Q5.6(iii): Using IUPAC norms write the formulas for the following: Diamminedichloridoplatinum(II)
- Q5.6(iv): Using IUPAC norms write the formulas for the following: Potassium tetracyanidonickelate(II)
- Q5.6(ix): Using IUPAC norms write the formulas for the following: Tetrabromidocuprate(II)
- Q5.6(v): Using IUPAC norms write the formulas for the following: Pentaamminenitrito-O-cobalt(III)
- Q5.6(vi): Using IUPAC norms write the formulas for the following: Hexaamminecobalt(III) sulphate
- Q5.6(vii): Using IUPAC norms write the formulas for the following: Potassium tri(oxalato)chromate(III)
- Q5.6(viii): Using IUPAC norms write the formulas for the following: Hexaammineplatinum(IV)
- Q5.6(x): Using IUPAC norms write the formulas for the following: Pentaamminenitrito-N-cobalt(III)
- Q5.7 (i): Using IUPAC norms write the systematic names: ([Co(NH_{3})_{6}]Cl_{3})
- Q5.7 (ii): Using IUPAC norms write the systematic names: ([Pt(NH_{3})_{2}Cl(NH_{2}CH_{3})]Cl)
- Q5.7 (iii): Using IUPAC norms write the systematic names: ([Ti(H_{2}O)_{6}]^{3+})
- Q5.7 (iv): Using IUPAC norms write the systematic names: ([Co(NH_{3})_{4}Cl(NO_{2})]Cl)
- Q5.7 (ix): Using IUPAC norms write the systematic names: ([Ni(CO)_{4}])
- Q5.7 (v): Using IUPAC norms write the systematic names: ([Mn(H_{2}O)_{6}]^{2+})
- Q5.7 (vi): Using IUPAC norms write the systematic names: ([NiCl_{4}]^{2-})
- Q5.7 (vii): Using IUPAC norms write the systematic names: ([Ni(NH_{3})_{6}]Cl_{2})
- Q5.7 (viii): Using IUPAC norms write the systematic names: ([Co(en)_{3}]^{3+})
- Q5.7(i): Using IUPAC norms write the systematic names of the following: \([Co(NH_{3})_{6}]Cl_{3}\)
- Q5.7(ii): Using IUPAC norms write the systematic names of the following: \([Pt(NH_{3})_{2}Cl(NH_{2}CH_{3})]Cl\)
- Q5.7(iii): Using IUPAC norms write the systematic names of the following: \([Ti(H_{2}O)_{6}]^{3+}\)
- Q5.7(iv): Using IUPAC norms write the systematic names of the following: \([Co(NH_{3})_{4}Cl(NO_{2})]Cl\)
- Q5.7(ix): Using IUPAC norms write the systematic names of the following: \([Ni(CO)_{4}]\)
- Q5.7(v): Using IUPAC norms write the systematic names of the following: \([Mn(H_{2}O)_{6}]^{2+}\)
- Q5.7(vi): Using IUPAC norms write the systematic names of the following: \([NiCl_{4}]^{2-}\)
- Q5.7(vii): Using IUPAC norms write the systematic names of the following: \([Ni(NH_{3})_{6}]Cl_{2}\)
- Q5.7(viii): Using IUPAC norms write the systematic names of the following: \([Co(en)_{3}]^{3+}\)
- Q5.8: List various types of isomerism possible for coordination compounds, giving an example of each.
- Q5.8: List various types of isomerism possible for coordination compounds, giving an example of each.
- Q5.9 (i): How many geometrical isomers are possible? ([Cr(C_{2}O_{4})_{3}]^{3-})
- Q5.9 (ii): How many geometrical isomers are possible? ([Co(NH_{3})_{3}Cl_{3}])
- Q5.9(i): How many geometrical isomers are possible in the following coordination entities? \([Cr(C_{2}O_{4})_{3}]^{3-}\)
- Q5.9(ii): How many geometrical isomers are possible in the following coordination entities? \([Co(NH_{3})_{3}Cl_{3}]\)
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