Lecture PowerPoint

Chemistry
The Molecular N ature of
Matter and Change
F ifth Edition

Martin S. Silberberg

1 Copyright  The McGraw-Hill Companies, Inc. Permission required for reproduction or display.
 Chapter 2 3

The Transition Elements and Their Coordination

Compounds

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 The Transition Elements and Their Coordination Compounds

2 3 .1 Properties of the Transition Elements

2 3 .2 The Inner Transition Elements

2 3 .3 Highlights of Selected Transition Metals

2 3 .4 Coordination Compounds

2 3 .5 Theoretical Basis for the Bonding and Properties of Complexes

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 F igure 2 3 .1 The transition elements (d b lock) and inner transition
elements (f b lock) in the periodic tab le.

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 F igure 2 3 .2 The Period 4 transition metals.

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 Sample Prob lem 2 3 .1 W riting Electron Configurations of Transition Metal
A toms and Ions

PR O BLEM: W rite condensed electron configurations for the following: (a) Z r;

(b ) V 3 + ;(c) Mo3 + . (A ssume that elements in higher periods
b ehave like those in Period 4 .)
PLA N : The general configuration is [nob le gas] ns2 (n - 1 )dx. R ecall that in
ions the ns electrons are lost first.

SO LU TIO N :
(a) Z r is the second element in the 4 d series: [K r]5 s2 4 d2 .
(b ) V is the third element in the 3 d series: [A r]4 s2 3 d3 . In forming V 3 + , three
electrons are lost (two 4 s and one 3 d), so V 3 + is a d2 ion: [A r]3 d2 .
(c) Mo lies b elow Cr in Group 6 B(6 ), so we expect the same exception
configuration as for Cr. Thus, Mo is [K r]5 s1 4 d5 . In forming the ion, Mo3 +
loses the one 5 s and two of the 4 d electrons to b ecome a 4 d3 ion: [K r]4 d3 .

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 F igure 2 3 .3 Horizontal trends in key atomic properties of the Period 4
elements.

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 F igure 2 3 .4
V ertical trends in key properties within the transition elements.

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 F igure 2 3 .5 A queous oxoanions of transition elements.

O ne of the most characteristic

chemical properties of these
elements is the occurrence of
multiple oxidation states.

Mn2 + MnO 4 2 − MnO 4 −

MnO 4 −
Cr2 O 7 2 −
V O 43−

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 F igure 2 3 .6

Colors of representative compounds of the Period 4 transition metals.

sodium nickel(II) nitrate
chromate hexahydrate
potassium zinc sulfate
Titanium(IV ) oxide
ferricyanide heptahydrate

scandium oxide manganese(II) copper(II)

chloride sulfate
vanadyl sulfate tetrahydrate cob alt(II) pentahydrate
dihydrate chloride
hexahydrate

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 Sample Prob lem 2 3 .2 F inding the N umb er of U npaired Electrons

PR O BLEM: The alloy SmCo5 forms a permanent magnet b ecause b oth

samarium and cob alt have unpaired electrons. How many
unpaired electrons are in the Sm atom (Z = 6 2 )?

PLA N : W rite the condensed configuration of Sm and, using Hund’s rule

and the aufb au principle, place electrons into a partial orb ital
diagram.

SO LU TIO N : Sm is the eighth element after X e. Two electrons go into the 6s

sub level and the remaining six electrons into the 4 f (which fills
b efore the 5 d).
Sm is [X e]6 s2 4 f6

6s 4f 5d

There are 6 unpaired e− in Sm.

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 F igure The b right colors of chromium (V I) compounds.
2 3 .7

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F igure 2 3 .8 Steps in producing a b lack-and-white negative.

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 F igure 2 3 .9 Components of a coordination compound.

models wedge diagrams chemical

formulas

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 Structures of Complex Ions:
Coordination N umb ers, Geometries, and Ligands

•Coordination numb er - the numb er of ligand atoms that are b onded

directly to the central metal ion. The coordination numb er is specific for
a given metal ion in a particular oxidation state and compound.

•Geometry - the geometry (shape) of a complex ion depends on the

coordination numb er and nature of the metal ion.

•D onor atoms per ligand - molecules and/or anions with one or more
donor atoms that each donate a lone pair of electrons to the metal ion to
form a covalent b ond.

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 F igure 2 3 .2 2 The spectrochemical series.

•F or a given ligand, the color depends on the oxidation state of the metal ion.

•F or a given metal ion, the color depends on the ligand.

I- < Cl- < F - < O H- < H2 O < SCN - < N H3 < en < N O 2 - < CN - < CO

W EA K ER F IELD STR O N GER F IELD

SMA LLER  LA R GER 

LO N GER  SHO R TER 

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 Formulas of Coordination Compounds

R ules for writing formulas:

1 . The cation is written b efore the anion.

2 . The charge of the cation(s) is b alanced b y the charge

of the anion(s).

3 . In the complex ion, neutral ligands are written b efore

anionic ligands, and the formula for the whole ion is
placed in b rackets.

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 N ames of Coordination Compounds

R ules for naming complexes:

1 . The cation is named b efore the anion.

2 . W ithin the complex ion, the ligands are named, in alphab etical
order, before the metal ion.
3 . N eutral ligands generally have the molecule name, b ut there are a
few exceptions. A nionic ligands drop the -ide and add -o after the
root name.
4 . A numerical prefix indicates the numb er of ligands of a particular
type.
5 . The oxidation state of the central metal ion is given b y a R oman
numeral (in parentheses) only if the metal ion can have more than
one state, as in the compound named in rule 1 .
6 . If the complex ion is an anion we drop the ending of the metal
name and add -ate.

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 Sample Prob lem 2 3 .3 W riting N ames and F ormulas of Coordination
Compounds

PR O BLEM: (a) W hat is the systematic name of N a3 [A lF 6 ]?

(b ) W hat is the systematic name of [Co(en)2 Cl2 ]N O 3 ?
(c) W hat is the formula of tetraamineb romochloroplatinum(IV )
chloride?
(d) W hat is the formula of hexaaminecob alt(III) tetrachloro-
ferrate(III)?
PLA N : U se the rules presented - F ormulas and N ames .

SO LU TIO N : (a) The complex ion is [A lF 6 ]3 -.

Six (hexa-) fluorines (fluoro-) are the ligands - hexafluoro
A luminum is the central metal atom - aluminate

A luminum has only the + 3 ion so we don’t need R oman

numerals.

sodium
hexafluoroaluminate
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 Sample Prob lem 2 3 .3 W riting N ames and F ormulas of Coordination
Compounds

(b ) There are two ligands, chlorine and ethylenediamine -

dichloro, bis(ethylenediamine)
The complex ion is the cation and we have to use R oman numerals
for the cob alt oxidation state since it has more than one - (III)
The anion, nitrate, is named last.
dichlorobis(ethylenediamine)cobalt(II
I) nitrate
(c) 4 N H3 Br- Cl- Pt4 + Cl-

tetraammineb romochloroplatinum(IV ) chloride

[Pt(N H3 )4 BrCl]Cl2
(d) 6 N H3 Co3 + 4 Cl- F e3 +
hexaamminecob alt(III) tetrachloro-ferrate(III)

[Co(N H3 )6 ][Cl4 F e]3

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 F igure 2 3 .1 0
Important types of isomerism in coordination compounds.

ISO MER S
Same chemical formula, b ut different properties

Constitutional (structural) isomers Stereoisomers

A toms connected differently D ifferent spatial arrangement

Coordination Linkage isomers Geometric (cis- O ptical isomers

isomers trans) isomers (enantiomers)
D ifferent donor
(diastereomers)
Ligand and atom N onsuperimposab le
counter-ion D ifferent mirror images
exchange arrangement
around metal ion

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 Linkage isomers

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 F igure 2 3 .1 1 Geometric (cis-trans) isomerism.

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 F igure 2 3 .1 2

O ptical isomerism in an
octahedral complex ion.

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 Sample Prob lem 2 3 .4 D etermining the Type of Stereoisomerism

PR O BLEM: D raw all stereoisomers for each of the following and state the type
of isomerism:
(a) [Pt(N H3 )2 Br2 ] (b ) [Cr(en)3 ]3 + (en = H2 N CH2 CH2 N H2 )

PLA N : D etermine the geometry around each metal ion and the nature of
the ligands. Place the ligands in as many different positions as
possib le. Look for cis-trans and optical isomers.

SO LU TIO N : (a) Pt(II) forms a square planar complex and there are two pairs
of monodentate ligands - N H3 and Br.

These are geometric isomers;

they are not optical isomers
since they are superimposab le
on their mirror images.
trans cis

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 Sample Prob lem 2 3 .4 D etermining the Type of Stereoisomerism

(b ) Ethylenediamine is a b identate ligand. Cr3 + is hexacoordinated and

will form an octahedral geometry.
Since all of the ligands are identical, there will b e no geometric isomerism
possib le.

The mirror images are

nonsuperimposab le
and are therefore
optical isomers.

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 F igure 2 3 .1 3
Hyb rid orb itals and b onding in the octahedral [Cr(N H3 )6 ]3 + ion.

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 F igure 2 3 .1 4

Hyb rid orb itals and b onding in the square planar [N i(CN )4 ]2 - ion.

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 F igure 2 3 .1 5
Hyb rid orb itals and b onding in the tetrahedral [Z n(O H)4 ]2 - ion.

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 F igure 2 3 .1 6 A n artist’s wheel.

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 F igure 2 3 .1 7 The five d-orb itals in an octahedral field of ligands.

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 F igure 2 3 .1 8 Splitting of d-orb ital energies b y an octahedral field of
ligands.

 is the splitting energy

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 F igure 2 3 .1 9 The effect of the ligand on splitting energy.

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 F igure 2 3 .2 0 The color of [Ti(H2 O )6 ]3 + .

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 F igure 2 3 .2 1 Effects of the metal oxidation state and of ligand
identity on color.

[V (H2 O )6 ]2 + [V (H2 O )6 ]3 +

[Cr(N H3 )6 ]3 + [Cr(N H3 )5 Cl ]2 +

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 Sample Prob lem 2 3 .5 R anking Crystal F ield Splitting Energies for Complex
Ions of a Given Metal

PR O BLEM: R ank the ions [Ti(H2 O )6 ]3 + , [Ti(N H3 )6 ]3 + , and [Ti(CN )6 ]3 - in terms of

the relative value of  and of the energy of visib le light ab sorb ed.

PLA N : The oxidation state of Ti is 3 + in all of the complexes so we are

looking at the crystal field strength of the ligands. The stronger the
ligand the greater the splitting and the higher the energy of the light
ab sorb ed.

SO LU TIO N : The field strength according to is CN - > N H3 > H2 O . So the

relative values of  and energy of light ab sorb ed will b e

[Ti(CN )6 ]3 - > [Ti(N H3 )6 ]3 + > [Ti(H2 O )6 ]3 +

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 F igure 2 3 .2 3 High-spin and low-spin complex ions of Mn2 + .

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 F igure 2 3 .2 4 O rb ital occupancy for high-spin and low-spin complexes of
d4 through d7 metal ions.

high spin: low spin: high spin: low spin:

weak-field strong- weak-field strong-
ligand field ligand field
ligand ligand

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 Sample Prob lem 2 3 .6 Identifying Complex Ions as High Spin or Low Spin

PR O BLEM: Iron (II) forms an essential complex in hemoglob in. F or each of the
two octahedral complex ions [F e(H2 O )6 ]2 + and [F e(CN )6 ]4 -, draw an
orb ital splitting diagram, predict the numb er of unpaired electrons,
and identify the ion as low or high spin.

PLA N : The electron configuration of F e2 + gives us information that the

iron has 6 d electrons. The two ligands have field strengths shown
in F igure 2 3 .2 2 .
D raw the orb ital b ox diagrams, splitting the d orb itals into eg and
t2 g. A dd the electrons noting that a weak-field ligand gives the
maximum numb er of unpaired electrons and a high-spin complex
and vice-versa.
[F e(CN )6 ]4 -
SO LU TIO N : [F e(H2 O )6 ]2 +
potential energy

4 unpaired e-- eg
(high spin)
eg no unpaired e--
(low spin)
t2 g
t2 g
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 F igure 2 3 .2 5 Splitting of d-orb ital energies b y a
tetrahedral field of ligands.

tetrahedral

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F igure 2 3 .2 6 Splitting of d-orb ital energies b y a square planar field of
ligands.

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 F igure B2 3 .1 Hemoglob in and the octahedral complex in heme.

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 F igure B2 3 .2 The tetrahedral Z n2 + complex in carb onic anhydrase.

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