Problem 2
Write down the ground state electronic configurations of the following atoms and ions: (a) \(\mathrm{Fe}\) (b) \(\mathrm{Fe}^{3+} ;\) (c) \(\mathrm{Cu} ;(\mathrm{d}) \mathrm{Zn}^{2+} ;\) (e) \(\mathrm{V}^{3+} ;\) (f) \(\mathrm{Ni} ;(\mathrm{g})\) \(\mathrm{Cr}^{3+} ;(\mathrm{h}) \mathrm{Cu}^{+}\).
Problem 4
What is the oxidation state of the metal in the following complexes? (a) \(\left[\mathrm{CoCl}_{4}\right]^{2-}\) (b) \(\left[\mathrm{Fe}(\mathrm{CN})_{6}\right]^{3-}\) (c) \(\left[\mathrm{Ni}(\operatorname{gly}-N, O)_{3}\right]^{-}\) \((\mathrm{d})\left[\mathrm{Fe}(\mathrm{bpy})_{3}\right]^{3+}\) (e) \(\left[\mathrm{Cr}(\operatorname{acac})_{3}\right]\) \((\mathrm{f})\left[\mathrm{Co}\left(\mathrm{H}_{2} \mathrm{O}\right)_{6}\right]^{2+}\) \((g)\left[\mathrm{Ni}(\mathrm{en})_{3}\right]^{2+}\) (h) \([\mathrm{Ni}(\text { edta })]^{2-}\) (i) \(\left[\mathrm{Cu}(\mathrm{ox})_{2}\right]^{2-}\) \((j)\left[\mathrm{Cr}(\mathrm{en})_{2} \mathrm{F}_{2}\right]^{+}\)
Problem 5
Use the Kepert theory to suggest structures for the following complexes. Could any of these complexes possess stereoisomers? If so, suggest which isomer might be favoured (none of the 4-coordinate complexes is square planar): (a) \(\left[\mathrm{Zn}(\mathrm{OH})_{4}\right]^{2-}\) (b) \(\left[\mathrm{Ru}\left(\mathrm{NH}_{3}\right)_{5}(\mathrm{NCMe})\right]^{2+}\) (c) \(\left[\operatorname{CoBr}_{2}\left(\operatorname{PPh}_{3}\right)_{2}\right]\) (d) \(\left[\mathrm{WBr}_{4}(\mathrm{NCMe})_{2}\right]\) (e) \(\left[\operatorname{Re} \mathrm{Cl}(\mathrm{CO})_{3}(\mathrm{py})_{2}\right]\) \((\mathrm{f})\left[\mathrm{Cr}\left(\mathrm{NPr}_{2}\right)_{3}\right]\) \((\mathrm{g})\left[\mathrm{Cr} \mathrm{Cl}_{3}\left(\mathrm{NMe}_{2}\right)_{2}\right]\)
Problem 6
Estimate the charge distribution over the metal and donor atoms in the complex ions (a) \(\left[\mathrm{Fe}(\mathrm{bpy})_{3}\right]^{2+}\) and (b) \(\left[\mathrm{CrF}_{6}\right]^{3-}\).
Problem 7
Draw the stereoisomers of (a) octahedral \(\left[\mathrm{Mn}\left(\mathrm{H}_{2} \mathrm{O}\right)_{2}(\mathrm{ox})_{2}\right]^{2-},(\mathrm{b})\) octahedral \(\left[\mathrm{Co}\left(\mathrm{H}_{2} \mathrm{O}\right)\left(\mathrm{NH}_{3}\right)(\mathrm{en})_{2}\right]^{3+},(\mathrm{c})\) square planar \(\left[\mathrm{NiCl}_{2}\left(\mathrm{PMe}_{3}\right)_{2}\right]\) and (d) octahedral \(\left[\mathrm{Cr} \mathrm{Cl}_{3}(\text { dien })\right]\).
Problem 8
Draw the structures of the isomers of octahedral \(\left[\mathrm{Ni}(\mathrm{gly})_{3}\right]^{-}\).
Problem 9
Which of the following octahedral complexes possess enantiomers? (a) \(\left[\mathrm{Fe}(\mathrm{ox})_{3}\right]^{3-}\) (b) \(\left[\mathrm{Fe}(\mathrm{en})\left(\mathrm{H}_{2} \mathrm{O}\right)_{4}\right]^{2+}\) (c) \(c i s-\left[\mathrm{Fe}(\mathrm{en})_{2}\left(\mathrm{H}_{2} \mathrm{O}\right)_{2}\right]^{2+}\) (d) \(\operatorname{trans}-\left[\mathrm{Fe}(\mathrm{en})_{2}\left(\mathrm{H}_{2} \mathrm{O}\right)_{2}\right]^{2+}\) (e) \(\left[\mathrm{Fe}(\text { phen })_{3}\right]^{3+}\) (f) \(\left[\mathrm{Co}(\text { bpy })(\mathrm{CN})_{4}\right]^{-}\)
Problem 11
(a) What is the oxidation state of Cr in \(\left[\mathrm{CrCl}_{2}\left(\mathrm{H}_{2} \mathrm{O}\right)_{4}\right] \mathrm{Cl} \cdot 2 \mathrm{H}_{2} \mathrm{O} ?(\mathrm{b})\) Draw the structures of the isomers of the complex cation \(\operatorname{in}\left[\mathrm{CrCl}_{2}\left(\mathrm{H}_{2} \mathrm{O}\right)_{4}\right] \mathrm{Cl} \cdot 2 \mathrm{H}_{2} \mathrm{O}\). (c) What other types of isomerism may \(\left[\mathrm{CrCl}_{2}\left(\mathrm{H}_{2} \mathrm{O}\right)_{4}\right] \mathrm{Cl} \cdot 2 \mathrm{H}_{2} \mathrm{O}\) exhibit?
Problem 12
Both tpy and dien act as tridentate ligands. Discuss possible isomerism in complexes of the type \(\left[\mathrm{M}(\operatorname{tp} \mathrm{y})_{2}\right]^{2+}\) and \(\left[\mathrm{M}(\operatorname{dien})_{2}\right]^{2+}\).
Problem 13
Suggest possible products (including isomers if appropriate) for the following reactions: (a) \(\left[\mathrm{Ni}\left(\mathrm{H}_{2} \mathrm{O}\right)_{6}\right]^{2+}+3 \mathrm{en} \rightleftharpoons\) (b) \(\left[\mathrm{Co}\left(\mathrm{H}_{2} \mathrm{O}\right)_{6}\right]^{2+}+3\) phen \(\rightleftharpoons\) (c) \(\mathrm{VCl}_{4}+2 \mathrm{py} \rightleftharpoons\) (d) \(\left[\mathrm{Cr}\left(\mathrm{H}_{2} \mathrm{O}\right)_{6}\right]^{3+}+3[\mathrm{acac}]^{-} \rightleftharpoons\) (e) \(\left[\mathrm{Fe}\left(\mathrm{H}_{2} \mathrm{O}\right)_{6}\right]^{2+}+6[\mathrm{CN}]^{-} \rightleftharpoons\) (f) \(\mathrm{FeCl}_{2}+6 \mathrm{NH}_{3} \rightleftharpoons\)
