Determine the number of unpaired electrons expected for \({\left( {{\rm{Fe}}{{\left( {{\rm{N}}{{\rm{O}}_2}} \right)}_6}} \right)^{3 - }}\)and for \({\left( {Fe{F_6}} \right)^{3 - }}\)in terms of crystal field theory.

Short Answer

Expert verified

First we have\({\left( {{\rm{Fe}}{{\left( {{\rm{N}}{{\rm{O}}_2}} \right)}_6}} \right)^{3 - }}\), where the central atom is the transition metal iron which is attached with \(6\) nitrate ions.

Step by step solution

01

0f 4: oxidation state of \(Fe\)

  • Let us determine the oxidation state of \(Fe\)as we use \(x\) for the oxidation state of \(Fe\)We know that general oxidation state of nitrate ion is \( - 1,\)
  • Hence, we can determine the oxidation state of \(Fe\)like this:

\(\begin{align}{}x + (6 \cdot - 1) &= - 3\\x - 6 = - 3\\x &= - 3 + 6\\x &= + 3\end{align}\)

  • It means the oxidation state of \(Fe\)is \( + 3.\)
  • If we look at the periodic table we can see that the atomic number of Fe is 26 and its electronic configuration is\((Ar)3{d^6}4{s^2}\)
  • In oxidation state of \(F{e^{3 + }}\)the electronic configuration is: \((Ar)3{d^5}4{s^0}.\)

02

of 4: Explanation of electron pairs

  • We know that ligand contributes a pair of electrons to the metal and since \({\rm{N}}{{\rm{O}}_2}\)is a strong field ligand hence, it causes larger splitting.
  • The magnitude of pairing energy \(\left( P \right)\)is less than crystal field splitting energy in octahedral field: \(P < {\Delta _o}\)which means the electron pairs donated by ligand go to the innermost orbitals.
  • From the crystal field diagram we can see that \({\left( {{\rm{Fe}}{{\left( {{\rm{N}}{{\rm{O}}_2}} \right)}_6}} \right)^{3 - }}\)has unpaired electron.

03

of 4: oxidation state

  • In\({\left( {{\rm{Fe}}{{\rm{F}}_6}} \right)^{3 - }}\), the central atom is the transition metal iron which is attached with \(6\) fluoride ions.
  • We can determine the oxidation state of \(Fe\)as by using\(x\)for the oxidation state of \(Fe\).
  • As we know that general oxidation state of fluoride ion is \( - 1\),let us determine the oxidation state of \(Fe\)like this:

\(\begin{align}{}x + (6 \cdot - 1) &= - 3\\x - 6 &= - 3\\x& = - 3 + 6\\x &= + 3\end{align}\)

  • It means that the oxidation state of \(Fe\)is \( + 3.\)
  • As per the periodic table, the atomic number of \(Fe\) is \(26\) and its electronic configuration is \((Ar)3{d^6}4{s^2}.\)
  • In oxidation state of \(F{e^{3 + }}\),the electronic configuration is: \((Ar)3{d^5}4{s^0}.\)

04

of 4:Splitting of ligand

  • The ligand contributes a pair of electrons to the metal and since \({F^ - }\)is a weak field ligand hence, it causes smaller splitting.
  • The magnitude of pairing energy \((P)\)is bigger than crystal field splitting energy in octahedral field: \({\bf{P}} > {\Delta _a},\)which means that the electron pairs donated by ligand go to the outermost orbitals.
  • We could conclude from the crystal field diagram that \({\left( {{\rm{Fe}}{{\rm{F}}_6}} \right)^{3 - }}\)has 5 unpaired electrons.

Result

\({\left( {{\rm{Fe}}{{\left( {{\rm{N}}{{\rm{O}}_2}} \right)}_6}} \right)^{3 - }}\)has\(1\)unpaired electron and \({\left( {{\rm{Fe}}{{\rm{F}}_6}} \right)^{3 - }}\)has \(5\)unpaired electrons.

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Most popular questions from this chapter

Predict the products of each of the following reactions and then balance the chemical equations.

(a) Fe is heated in an atmosphere of steam.

(b) NaOH is added to a solution of Fe(NO3)3.

(c) FeSO4 is added to an acidic solution of KMnO4.

(d) Fe is added to a dilute solution of H2SO4.

(e) A solution of Fe(NO3)2 and HNO3 is allowed to stand in air.

(f) FeCO3 is added to a solution of HClO4.

(g) Fe is heated in air.

Predict whether the carbonate ligand \(C{O_3}^2\)- will coordinate to a metal center as a monodentate, bidentate, or tridentate ligand.

Give the coordination numbers and write the formulas for each of the following, including all isomers where appropriate:

(a) tetrahydroxozincate(II) ion (tetrahedral)

(b) hexacyanopalladate(IV) ion

(c) dichloroaurate(I) ion (note that aurum is Latin for “gold”)

(d) diamminedichloroplatinum(II)

(e) potassium diamminetetrachlorochromate(III)

(f) hexaamminecobalt(III) hexacyanochromate(III)

(g) dibromobis(ethylenediamine) cobalt(III) nitrate

Would you expect the complex \(\left( {Co{{(en)}_3}} \right)C{l_3}\) to have any unpaired electrons? Any isomers?

Give the oxidation state of the metal for each of the following oxides of the first transition series. (Hint: Oxides of formula M3O4 are examples of mixed valence compounds in which the metal ion is present in more than one oxidation state. It is possible to write these compound formulas in the equivalent format MO∙M2O3, to permitestimation of the metal’s two oxidation states.)

(a) Sc2O3

(b) TiO2

(c) V2O5

(d) CrO3

(e) MnO2

(f) Fe3O4

(g) Co3O4

(h) NiO

(i) Cu2O

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