Class-work-Inorganic Chemistry II

Electronic Spectroscopy
1. Name and draw structures of the following complexes: (a) [Ni(CO) 4], (b) [Ni(CN)4]2-,
(c) [CoCl4]2-, (d) [Mn(NH3)6]2+, e) [Pt(NH3)2(ox)], [PdBrCl(PEt3)2], g) [IrH(CO)(PPh3)2].

2. Give formulas for (a) chloridopentaamminecobalt(III) chloride, (b) hexaaquairon(3+)

nitrate, (c) cis-dichloridobis(ethylenediamine)ruthenium(II), (d) μ-
hydroxidobis(penta-amminechromium(III)) chloride.

3. Suggest why (a) high coordination numbers are

not usual for first row d-block metals, (b) in early d-block metal complexes the
combination of a high oxidation state and high coordination number is common,
and (c) in first row d-block metal complexes, high oxidation states are stabilized by
fluoro or oxo ligands

4. Suggest a structure for the complex [CuCl(L)]+ assuming that all donor atoms are
coordinated to the Cu(II) center:

L=

5. Which of the following octahedral complexes are chiral: cis-[CoCl2(en)2]+, [Cr(ox)3]3+,

trans-[PtCl2(en)2]2+, [Ni(phen)3]2+, [RuBr4(phen)]-, cis-[RuCl(py)(phen)2]+?

6. Using spectroscopic methods, how would you distinguish between the pairs of
isomers (a) cis- and trans-[PdCl2(PPh3)2], (b) cis- and trans-[PtCl2(PPh3)2] and
c) fac- and mer-[RhCl3(PMe3)3]

7. A pink solid has the formula CoCl3.5NH3.H2O. A solution of this salt is also pink and
rapidly gives three 3 mol AgCl on titration with silver nitrate solution. When the pink
solid is heated, it loses 1 mol H2O to give a purple solid with the same ratio of
NH3:Cl:Co. The purple solid, on dissolution and titration with AgNO3, releases two of
its chlorides rapidly. Deduce the structures of the two octahedral complexes and
draw and name them.
8. State the types of isomerism that may be exhibited by the following complexes, and
draw structures of the isomers:
a) [Co(en)2(ox)]+, b) [Cr(ox)2(OH2)2]-, c) [PtCl2(PPh3)2], d) [PtCl2(Ph2PCH2CH2PPh2)]
and e) [Co(en)(NH3)2Cl2]2+

9. The reaction of [ZrCl4(dppe)] (dppe is a bidentate phosphine ligand) with Mg(CH3)2

gives [Zr(CH3)4(dppe)]. NMR spectra indicate that all methyl groups are equivalent.
Draw octahedral and trigonal prism structures for the complex and show how the
conclusion from NMR supports the trigonal prism assignment.
10. Explain why the following complex is chiral:

11. Assuming the displacement of a water by a ligand were so favored that the back
reaction could be ignored, calculate all the stepwise formation constants you would
expect in the formation of [ML6]2+ from [M(OH2)6]2+, and the overall formation
constant, given that Kf1 = 1 x 105.
12. The stepwise formation constants for complexes of NH3 with [Cu(OH2)6]2+(aq) are
log Kf1 = 4.15, log Kf2 = 3.50, log Kf3 = 2.89, log Kf4 = 2.13, and log Kf5 = -0.52. Suggest
a reason why Kf5 is so different.