UP Academic League of Chemical Engineering Students (UP ALCHEMES)

Academic Affairs Committee - Reviews and Tutorials Series, A.Y. 2015-2016

Chem 17 Special Review - Complex Ions (ANSWER KEY)

I. 1. tetrachloroaurate(III) ion
2. tetraaquadithiocyanato-S-iron(III) ion
3. diamminetetrachlorochromate(III) ion
4. bis(ethylenediamine)dinitrito-O-cobalt(III) ion
5. dihydroxodifluorocuprate(II) ion
6. tetracarbonylnickel(0)
7. potassium hexacyanoferrate(II)
8. hexaaquaaluminum(III) dithiosulfatoargentate(I)
9. tris(ethylenediamine)copper(II)
tetraiodomercurate(II)
10. tetraammineoxalatocobalt(III)
ethylenediaminetetraacetatoplumbate(II) 4. paramagnetic

II. 1. [CrI(H2O)4(NH3)]2+
2. Na2[Fe(CN)4(H2O)2]
3. [Fe(OH)(SCN)(H2O)4][SnCl3(H2O)]
4. [NiBr(CO)3]3[Co(NCS)2(SO4)2]
5. [Co(OH)(en)2(NH3)]3[Cr(ONO)2(ox)2]2

III. 1. diamagnetic

5. diamagnetic

2. paramagnetic

IV. 1. ionization
2. coordination
3. linkage
3. paramagnetic 4. geometric
5. optical
V. 1. a.

b.
2. a. left: trans-; right: cis-
b. left: fac-; right: mer-
3. a. A and F; C and E; B and D
b. A and F; C and E
c. No
4. red - [Co(H2O)(NH3)5]3+
yellow - [Co(CN)6]3-
orange - [Co(NH3)6]3+
violet - [CoCl(NH3)5]2+
5. a. [CrCl2(H2O)4]+
b. [Cr(H2O)6]3+
c. inert
I. Name the following compounds/ions given the chemical formula.
1 [AuCl4]-
Identify the ligands and the number of ligands
Ligand Qty Prefix Name
Cl -
4 tetra chloro
Ligand part: tetrachloro

Identify the charge of metal ion

z Au +4 z =z total
Cl
z Au +4 (1 )=(1 )
z Au =+ 3

The complex is an anion because the overall charge is negative. Use "aurate" instead of "gold"

Metal part: aurate(III)

ANS: tetrachloroaurate(III) ion

2 [Fe(SCN)2(H2O)4]+
Identify the ligands and the number of ligands
Ligand Qty Prefix Name
H2O 4 tetra aqua
SCN -
2 di thiocyanato-S-*
Ligand part: tetraaquadithiocyanato-S-
Note: The order should be alphabetical with respect to the names of the ligands. Prefixes are ignored when
alphabetizing. "Tetraaqua" comes first because "aqua" comes before "thiocyanato-S-" despite "di-" coming before
"tetra-"
* The S atom from SCN- attaches to the metal center

Identify the charge of metal ion

z Fe +4 z H O+ 2 z SCN =z total
2

z Fe +4 (0 )+2 (1 )=+ 1
z Fe =+ 3

The complex is an cation because the overall charge is positive. Use the unmodified name of the metal.

Metal part: iron(III)

ANS: tetraaquadithiocyanato-S-iron(III) ion

3 [CrCl4(NH3)2]-
Identify the ligands and the number of ligands
Ligand Qty Prefix Name
Cl- 4 tetra chloro
NH3 2 di ammine*
Ligand part: diamminetetrachloro
* Ammine is spelled with two m's

Identify the charge of metal ion

z Cr + 4 z +2 z NH =z total
Cl 3

z Cr + 4 (1 )+ 2(0)=- 1
z Cr =+ 3
The complex is an anion because the overall charge is negative. Use "chromate" instead of "chromium"

Metal part: chromate(III)

ANS: diamminetetrachlorochromate(III) ion

4 [Co(ONO)2(en)2]+
Identify the ligands and the number of ligands
Ligand Qty Prefix Name
en 2 bis* ethylenediamine
ONO- 2 di nitrito-O-
Ligand part: bis(ethylenediamine)dinitrito-O-
*Use "bis-" instead of "di-" because "ethylenediamine" already carries a prefix
When the nitrite ion is written as ONO-, it is the O atom that connects to the metal center.

Identify the charge of metal ion

z Co+2 z en +2 zONO =z total
z Co+2(0 )+2(1)=+1
z Co =+ 3

The complex is an cation because the overall charge is positive. Use the unmodified name of the metal.

Metal part: cobalt(III)

ANS: bis(ethylenediamine)dinitrito-O-cobalt(III) ion

5 [CuF2(OH)2]2-
Identify the ligands and the number of ligands
Ligand Qty Prefix Name
F- 2 di fluoro
OH -
2 di hydroxo
Ligand part: dihydroxodifluoro

Identify the charge of metal ion

z Cu +2 z F +2 z OH =z total
z Cu +2(1)+2(1)=- 2
z Cu =+2

The complex is an anion because the overall charge is negative. Use "cuprate" instead of "copper"

Metal part: cuprate(II)

ANS: dihydroxodifluorocuprate(II) ion

6 [Ni(CO)4]
Identify the ligands and the number of ligands
Ligand Qty Prefix Name
CO 4 tetra carbonyl
Ligand part: tetracarbonyl

Identify the charge of metal

 z Ni +4 z CO=z total
z Ni +4 (0)=0
z Ni =0

The complex is neutral. Use the unmodified name of the metal.

Metal part: nickel(0)

ANS: tetracarbonylnickel(0)

7 K4[Fe(CN)6]
Cation: potassium

Anion:
Fe can either have a +2 or +3 charge. Determine the overall charge of the complex.
4 z K + +z complex =0
4 (1)+z complex =0
z complex =- 4

Identify the ligands and the number of ligands

Ligand Qty Prefix Name
CN- 6 hexa cyano
Ligand part: hexacyano

Identify the charge of metal ion

z Fe +6 z CN =z total
z Fe +6(1)=(4 )
z Fe =+ 2

Use "ferrate" instead of "iron" (anion)

Metal part: ferrate(II)

Anion name: hexacyanoferrate(II)

ANS: potassium hexacyanoferrate(II)

8 [Al(H2O)6][Ag(S2O3)2]
Aluminium and silver have known charges of +3 and +1 respectively.

Cation:

Identify the ligands and the number of ligands

Ligand Qty Prefix Name
H2O 6 hexa aqua
Ligand part: hexaaqua

Identify the charge of metal ion: +3

Use the unmodified name of the metal (cation)

Metal part: aluminum(III)

Cation name: hexaaquaaluminum(III)

Anion:

Identify the ligands and the number of ligands

Ligand Qty Prefix Name
S2O32- 2 di thiosulfato
Ligand part: dithiosulfato

Identify the charge of metal ion: +1

Use "argentate" instead of "silver" (anion)

Metal part: argentate(I)

Anion name: dithiosulfatoargentate(I)

ANS: hexaaquaaluminum(III) dithiosulfatoargentate(I)

9 [Cu(en)3][HgI4]
Copper can have a +1 or +2 charge
Mercury can have a +1 or +2 charge
Use trial and error to determine the correct charges
If Cu has a +1 charge, Hg will end up with a +3 charge which is incorrect
Therefore, the charge of Cu is +2 and Hg is +2

Cation:

Identify the ligands and the number of ligands

Ligand Qty Prefix Name
en 3 tris* ethylenediamine
Ligand part: tris(ethylenediamine)
*Use "tris-" instead of "tri-" because "ethylenediamine" already carries a prefix

Identify the charge of metal ion: +2

Use the unmodified name of the metal (cation)

Metal part: copper(II)

Cation name: tris(ethylenediamine)copper(II)

Anion:

Identify the ligands and the number of ligands

Ligand Qty Prefix Name
I- 4 tetra iodo
Ligand part: tetraiodo

Identify the charge of metal ion: +2

Use "mercurate" instead of "mercury" (anion)

Metal part: mercurate(II)

Anion name: tetraiodomercurate(II)

ANS: tris(ethylenediamine)copper(II) tetraiodomercurate(II)

10 [Co(ox)(NH3)4]2[Pb(EDTA)]
Cobalt can have a +2 or +3 charge
Lead can have a +2 or +4 charge
Use trial and error to determine the correct charges
If Co has a +2 charge, Pb will have a +4 charge but the cation and anion will be neutral
Therefore, the charge of Co is +3 and Pb is +2

Cation:

Identify the ligands and the number of ligands

Ligand Qty Prefix Name
NH3 4 tetra tetraammine
ox 1 - oxolato
Ligand part: tetraammineoxolato

Identify the charge of metal ion: +3

Use the unmodified name of the metal (cation)

Metal part: cobalt(III)

Cation name: tetraammineoxalatocobalt(III)

Anion:

Identify the ligands and the number of ligands

Ligand Qty Prefix Name
EDTA 1 - ethylenediaminetetraacetato
Ligand part: ethylenediaminetetraacetato

Identify the charge of metal ion: +2

Use "plumbate" instead of "lead"

Metal part: plumbate(II)

Anion name: ethylenediaminetetraacetatoplumbate(II)

ANS: tetraammineoxalatocobalt(III) ethylenediaminetetraacetatoplumbate(II)

II. Give the chemical formula of the following compounds/ions.

1 amminetetraaquaiodochromium(III) ion
Metal Part: Cr3+

Identify ligands and number of ligands present

Prefix + Name Ligand Qty
ammine NH3 1
tetraaqua H2O 4
iodo I 1
Ligand Part: I(H2O)4(NH3)
Note: When writing the chemical formula, list down the anions before the neutral molecules. List down the species
in alphabetical order according to the first chemical symbol in their formulae. In this example, I - comes first
because it is an anion. H2O and NH3 come after because they are neutral molecules. Alphabetically, H comes first
before N, so H2O preceeds NH3

Calculate the overall charge

z total =z + z NH + 4 z H O + z I
Cr 3+ 3 2

z total =(3 )+(0 )+4 (0 )+(1)

z total =+ 2
Charge: +2

ANS: [CrI(H2O)4(NH3)]2+

2 sodium diaquatetracyanoferrate(II)
Cation: Na+

Anion:

Metal Part: Fe2+

Identify ligands and number of ligands present

Prefix + Name Ligand Qty
diaqua H2O 2
tetracyano CN 4
Ligand Part: (CN)4(H2O)2

Calculate the overall charge

z total =z +2 z H O + 4 z CN
Fe 2 + 2

z total =(2 )+ 2( 0)+ 4(1)

z total =-2
Charge: -2

Anion formula: [Fe(CN)4(H2O)2]2-

ANS: Na2[Fe(CN)4(H2O)2]

3 tetraaquahydroxothiosulfato-S-iron(III) aquatrichlorostannate(II)
Cation:

Metal Part: Fe3+

Identify ligands and number of ligands present

Prefix + Name Ligand Qty
tetraaqua H2O 4
hydroxo OH- 1
thiosulfato-S- SCN- 1
Ligand Part: (OH)(SCN)(H2O)4

Calculate the overall charge

z total=z +4 z H O + z OH + z SCN
Fe 3 + 2

z total=(3 )+4 (0 )+(1)+(1)

z total =+ 1
 Charge: +1

Cation formula: [Fe(OH)(SCN)(H2O)4]+

Anion:

Metal Part: Sn2+

Identify ligands and number of ligands present

Prefix + Name Ligand Qty
aqua H2O 1
trichloro Cl- 3
Ligand Part: Cl3(H2O)

Calculate the overall charge

z total =z + z H O +3 zCl
Sn 2 + 2

z total =(2 )+(0 )+ 3(1)

z total =- 1
Charge: -1

Anion formula: [SnCl3(H2O)]-

ANS: [Fe(OH)(SCN)(H2O)4][SnCl3(H2O)]

4 tricarbonylbromonickel(II) dithiosulfato-N-disulfatocobaltate(III)
Cation:

Metal Part: Ni2+

Identify ligands and number of ligands present

Prefix + Name Ligand Qty
tricarbonyl CO 3
bromo Br- 1
Ligand Part: Br(CO)3

Calculate the overall charge

z total =z Ni 2 ++ 3 z CO + z Br
z total =(2 )+ 3(0 )+(1)
z total =+ 1
Charge: +1

Cation formula: [NiBr(CO)3]+

Anion:

Metal Part: Co3+

Identify ligands and number of ligands present

Prefix + Name Ligand Qty
dithiocyanato-N- NCS- 2
disulfato SO42- 2
Ligand Part: (NCS)2(SO4)2
 Calculate the overall charge
z total =z +2 z NCS + 2 z SO 2
Co 3+ 4

z total =(3 )+2(1)+2(2)

z total =-3
Charge: -3

Anion formula: [Co(NCS)(SO4)]3-

ANS: [NiBr(CO)3]3[Co(NCS)2(SO4)2]

5 amminebis(ethylenediamine)hydroxocobalt(III) dinitrito-O-dioxolatochromate(III)
Cation:

Metal Part: Co3+

Identify ligands and number of ligands present

Prefix + Name Ligand Qty
ammine NH3 1
bis(ethylenediamine) en 2
hydroxo OH- 1
Ligand Part: (OH)(en)2(NH3)

Calculate the overall charge

z total =z + z NH +2 z en + z OH
Co 3+ 3

z total =(3 )+(0 )+2(0 )+(1)

z total =+ 2
Charge: +2

Cation formula: [Co(OH)(en)2(NH3)]2+

Anion:

Metal Part: Cr3+

Identify ligands and number of ligands present

Prefix + Name Ligand Qty
dinitrito-O- ONO- 2
dioxolato ox2- 2
Ligand Part: (ONO)2(ox)2

Calculate the overall charge

z total =z Cr 3+ +2 z ONO +2 z ox 2
z total =(3 )+2(1)+2(2)
z total =- 3
Charge: -3

Anion formula: [Cr(ONO)2(ox)2]3+

ANS: [Co(OH)(en)2(NH3)]3[Cr(ONO)2(ox)2]2

III. Draw an energy diagram of the d orbitals of the metal center of the following complexes then determine if the
complex is paramagnetic or diamagnetic.
1 [Fe(CN)6]4-
The charge of Fe in this complex is +2
Electron configuration of Fe2+: [Ar]3d6 6 electrons in d orbital
Note: Although 3d electrons are generally higher in energy, 4s electrons are removed first before 3d electrons

Geometry: octahedral dz2 and dx2-y2 higher in energy

Ligands are closer to these orbitals than the dxy, dyz, and dxz orbitals, so the energy of the dz2 and dx2-y2 increase.

Metal: Period 4 metal

Use spectrochemical series for octahedral complexes with a Period 4 metal

Ligand: CN- strong field ligand

Strong field ligands create a larger separation between the energy levels, so the lower energy level fills up first.

There are no unpaired electrons, so the complex is diamagnetic.

ANS: (diamagnetic)

2 [CrCl6]3-
The charge of Cr in this complex is +3
Electron configuration of Cr3+: [Ar]3d3 3 electrons in d orbital

Geometry: octahedral dz2 and dx2-y2 higher in energy

Metal: Period 4 metal

Use spectrochemical series for octahedral complexes with a Period 4 metal

Ligand: Cl- weak field ligand

Weak field ligands do not separate the energy levels to a great extent, so the higher energy orbitals fill up together
with the lower energy orbitals

There is at least one unpaired electron, so the complex is paramagnetic.

ANS: (paramagnetic)

3 [MoBr6]3-
The charge of Mo in this complex is +3
Electron configuration of Mo3+: [Kr]4d3 3 electrons in d orbital

Geometry: octahedral dz2 and dx2-y2 higher in energy

Metal: Period 5 metal

Octahedral complexes with a Period 5 or 6 metal are low spin complexes (have high splitting energy) regardless of
the ligands attached to it.

There is at least one unpaired electron, so the complex is paramagnetic.

ANS: (paramagnetic)

4 [Cu(NH3)4]2+
The charge of Cu in this complex is +2
Electron configuration of Cu2+: [Ar]3d9 9 electrons in d orbital

Geometry: tetrahedral dz2 and dx2-y2 lower in energy

Tetrahedral complexes are high spin (have low splitting energy) regardless of the ligands attached to it.

There is at least one unpaired electron, so the complex is paramagnetic.

ANS: (paramagnetic)

5 [NiCl4]2-
The charge of Ni in this complex is +2
Electron configuration of Ni2+: [Ar]3d8 8 electrons in d orbital

Geometry: square planar (d8 complexes are square planar)

Square planar complexes are low spin (have high splitting energy) regardless of the ligands attached to it.

There are no unpaired electrons, so the complex is diamagnetic.

ANS: (diamagnetic)

IV. Identify the kind of isomerism present in the following cases.

Complexes
1 [PtBr2(NH3)2]Cl2 vs [PtCl2(NH3)2]Br2
2 [Co(en)3][CrCl6] vs [Cr(en)3][CoCl6]
3 [Co(NO2)6]3- vs [Co(ONO)6]3-
4 cis-[PtCl2(NH3)2] vs trans-[PtCl2(NH3)2]
5 [CuBrClFI]2-

V. Problem Solving

1. Draw an energy diagram for diethylammonium tetrachlorocuprate(II) for the following conditions.
a. At low temperatures
b. At high temperatures

2. Identify the following

a. The cis- and the trans- isomer
ANS: left: trans-; right: cis-

b. The fac- and the mer- isomer

ANS: left: fac-; right: mer-

3. Consider the following complexes drawn below.

a. There are three pairs of identical compounds drawn above. Identify the pairs.

ANS: A and F; C and E; B and D

b. Two of the pairs are enantiomers. Idenfify the pairs.

ANS: A and F; C and E

c. Is the remaining pair optically active?

The mirror image of B or D is superimposable on the original.

ANS: No

4. While working in the laboratory, your lab partner prepared solutions of the following reagents: [Co(NH 3)6]3+,
[Co(H2O)(NH3)5]3+, [CoCl(NH3)5]2+, and [Co(CN)6]3-. Your partner, however, forgot to label the solutions. The colors of
the solutions, in no particular order, are red, yellow, orange, and violet. Determine which complex corresponds to
each color.

A compound of a given color absorbs light of the complementary color. The shorter the wavelength of the color, the
higher its energy level splitting.
Color of sol'n Color absorbed Energy*
red green 3
yellow violet 1
orange blue 2
violet yellow 4
* 1- highest; 4-lowest

Use the spectrochemical series to rank the energy level splitting of the complexes
Complex Energy
[Co(NH3)6]3+ 2
[Co(H2O)(NH3)5] 3+
3
[CoCl(NH3)5]2+ 4
[Co(CN)6]3- 1

ANS: red - [Co(H2O)(NH3)5]3+; yellow - [Co(CN)6]3-; orange - [Co(NH3)6]3+; violet - [CoCl(NH3)5]2+

5. Two sets of 50.0 mL 0.100 M CrCl3 are prepared simultaneously and were labeled S1 and S2. After preparation,
aqueous AgNO3 is added to S1 until precipitation stops. The precipitate is dried and weighed and its mass is
determined to be 0.717 g. S2 was left to stand for a week before AgNO 3 was added. This solution produced 2.15 g of
precipitate. (AgCl: M = 143.35 g/mol) Hint: Chromium has a coordination number of 6.
a. Determine the formula of the complex ion present in S1

Any Cl- that forms a complex with Cr3+ will not precipitate.

Calculate initial amount of Cl- in solution

3
nCrCl 3 =(0 . 0500 L )(0 .100 M )=5. 0000 10 mol
1 mol Cr 3 +
3
n 3 +=5 . 0000 10 M CrCl 3 =5 . 0000 103 mol Cr 3 +
Cr 1 mol CrCl 3

3 mol Cl
nCl =5 .0000 103 M CrCl 3 =0. 0150 mol Cl
1 mol CrCl 3

Calculate moles of Cl- that precipitated

0 .717 g
n AgCl = =5 . 0017 103 mol
143 .35 g/mol

3 1 mol Cl
nCl =5 .0017 10 mol AgCl =5 . 0017 103 mol Cl
1 mol AgCl
Calculate moles of Cl- bound to Cr3+ (not precipitated)
nCl =( 0 . 0150 mol )( 5 . 0017 103 mol)=9 . 9983 103 mol

Find ratio of Cl-(bound) to Cr3+

 3
9. 9983 10 mol
2
5. 0000 103 mol

ANS: [CrCl2(H2O)4]+

b. Determine the formula of the complex ion present in S2

Calculate moles of Cl- that precipitated

2. 15 g
n AgCl = =0 . 01500 mol
143 .35 g/mol
1 mol Cl
nCl =0 .01500 mol AgCl =0 .01500 molCl
1 mol AgCl
Calculate moles of Cl- bound to Cr3+ (not precipitated)
nCl =( 0 . 0150 mol )( 0 . 01500 mol )=1 .7440 106 mol

Find ratio of Cl-(bound) to Cr3+

6
1. 7440 10 mol
0
5 . 0000 103 mol

ANS: [Cr(H2O)6]3+

c. Is the complex in S1 labile or inert?

The Cl- in [CrCl2(H2O)4]+ took time to be replaced by H2O

ANS: inert