Transition Metals

TransitionMetals

Chapter22

TransitionMetals 1

Transition Metals: Occupy the d-block of periodic table

Have d-electrons in valence shell

SomecharacteristicsofTransitionMetalsandtheircompounds:

1. Exhibitmorethanoneoxidationstate
2. Theyformanextensiveseriesofcompoundsknownasmetal
complexes
l orcoordinationcompounds.
di ti d
3. Transitionmetalsexhibitinterestingmagneticproperties.
4. Manyoftheircompoundsarecolored.
5
5. Transition metals play important roles in biological systems and
Transitionmetalsplayimportantrolesinbiologicalsystems and
moderntechnology.
TransitionMetals 2
There are periodic trends in the transition metals,
but they are often complex
(product of several factors, some working in opposite
directions e.g.
e g combining the effects of increasing nuclear charge with
the presence of nonbonding d electrons)

Lanthanide contraction
similarity in size, behavior, &
properties
p p of 4d and 5d
transition elements
We wont worry about details of
periodic trends in the
transition metals or the exact
reasons for them

TransitionMetals 3

RecalltheElectronConfigurationsofthetransitionmetals.

Ar 3s23p6 Use th
U the periodic
i di table
t bl to
t gett electron
l t configurations
fi ti
of the First Row Transition metal ATOMS
K [Ar]4s1 Sc Zn
Ca [Ar]4s2
Sc [Ar]3d14s2
Ti [Ar]3d24s2
V
Cr
Mn
Fe
Co
Ni
Cu
Zn [Ar] 3d104s2

TransitionMetals 4
 Beabletofigureouttheelectronconfigurationof
transitionmetalions.
TransitionMetalscanhavemorethanoneoxidationstate.
Ti [Ar]3d24s2 Ni [Ar]3d84s2
Ti2+
Ti3+ Ni2+
Ti4+
Ti5+ Ni4+
Note: 4s is filled before 3d,
b t when
but h oxidized,
idi d
4s electrons are lost before 3d.

TransitionMetals 5

Some trends in Transition Metal Oxidation States

can be identified.
Oxidation States:
Highest oxidation states of Sc, Ti, V, Cr, Mn = number of valence
(4 + 3d) electrons.
(4s l t

Sc [Ar]3d14s2

Mn [[Ar]3d
] 54s2

Trend from Sc Mn:

The maximum oxidation state becomes increasingly unstable.
Sc3+, Ti4+ Are stable. Sc2O3 & TiO4 are stable oxides.
Mn 7+ E ists b
Exists butt is easil
easily red
reduced.
ced
MnO4 Strong oxidizing agent.
TransitionMetals 6
Manytransitionmetalsformcompoundsthathave
funcolors!
colorsareduetooxidationstateandelectron
g p
configuration...morespecificsaboutthatlater!

TransitionMetals 7

TransitionmetalsformCOMPLEXES.

Transition metal ions are Lewis acids

Ligands are Lewis bases

TransitionMetals 8
 Metalcomplex isformedwhenametalisbondedto
moleculesorions.

Complexion:metalcomplexthatisnotneutral

Coordinationcompounds:compoundsthatcontaincomplexes

Coordinationnumber:#ofatomsdirectlybondedtoametal

TransitionMetals 9

Thecoordinationoftheligandwiththemetalcangreatlyalter
itsphysicalorchemicalproperties

EXAMPLE:color

TransitionMetals 10
 ChemicalpropertiesofMetalComplexesdifferfrom
the properties of the metal alone
thepropertiesofthemetalalone.
Forexample:theeaseofoxidationofthemetalchangeswhena
metal complex forms
metalcomplexforms.

Which is easier to reduce, the metal ion or the complex?

Ag+(aq) + e Ag(s) E1/2= +0.80V

[Ag(CN)2](aq) + e Ag(s)+ 2CN(aq) E1/2 = 0.31V

TransitionMetals 11

ComplexesarecharacterizedbytheirOxidationStateandCoordination
Number,buttheidentityoftheligandsalsomatters.

OxidationState:primaryvalence

CoordinationNumber:secondaryvalence

EarlyFormula Color #ofIonsper FreeCl Ions ComplexionFormula

formula Unit inFormula
CoCl3 6NH3 orange 4 3 [Co(NH3)6]Cl3
CoCl3 5NH3 purple 3 2 [Co(NH3)5Cl]Cl2
CoCl3 4NH3 green 2 1 trans[Co(NH3)4Cl2]Cl
CoCl3 4NH3 violet 2 1 cis[Co(NH3)4Cl2]Cl

Thefourcompoundsinthetablebelowhavethesameoxidationstate
andcoordinationnumber,butclearlytheyhavedifferentproperties.
12
TransitionMetals
 CoordinationSphereisthecentralatom+ligandsbondedtoit
Use[]tosetoffcomponentsinthecoordinationsphere
[] p p

EarlyFormula Color #ofIonsper FreeCl Ions ComplexionFormula

formula Unit inFormula
in Formula
CoCl3 6NH3 orange 4 3 [Co(NH3)6]Cl3
CoCl3 5NH3 purple 3 2 [Co(NH3)5Cl]Cl2
CoCll3 4NH3 green 2 1 trans[Co(NH
[ ( 3)4Cll2]Cl
] l
CoCl3 4NH3 violet 2 1 cis[Co(NH3)4Cl2]Cl

Whathappenstothesecomplexeswhendissolvedinwater?

TransitionMetals 13

Knowingthechargeonacomplexionandthechargeoneachligand,
one can determine the oxidation number for the metal
onecandeterminetheoxidationnumberforthemetal.

[[Cu(NH
( 3)4]]SO4 K2[[Ni(CN)
( )4]]

Chargeonthecomplex: Chargeonthecomplex:

Coordination #:
Coordination#: Coordination#:

Oxidation state of the metal:

Oxidationstateofthemetal: Oxidationstateofthemetal:

TransitionMetals 14
 Or,knowingtheoxidationnumberonthemetalandthe
chargesontheligands,onecancalculatethechargeonthe
complexion.
Fe3+ surroundedbysixwatermolecules Pt(II)surroundedbytwoammonia
molecules and two bromide ions
moleculesandtwobromideions

Chargeonthecomplex: Chargeonthecomplex:

Coordinationnumber: Coordinationnumber:

TransitionMetals 15

GeometriesofTransitionMetalComplexes
Geometry for Coordination # = 4

Tetrahedral SquarePlanar
Square Planar

[Ni(CN)4]2-

[Zn(NH3)4]2+
2
[PtCl2(NH3)2]

TransitionMetals 16
 GeometriesofTransitionMetalComplexes
Geometryy for Coordination # = 5
Trigonal Bipyramidal

[Fe(CO)5]
[Re(SCH2C6H4OCH3-p)3(PPh3)2]
ReL3(PR3)2

TransitionMetals 17

GeometriesofTransitionMetalComplexes
Geometryy for Coordination # = 6
Octahedral
chromium(III)andcobalt(III)consistentlyhave
h i (III) d b lt(III) i t tl h
thesamecoordinationnumberof6

[CoF6]3
3

[Co(en)3]3+

TransitionMetals 18
 SpecialLigands:ChelatingAgents
Chelates are ligands possessing two or more donor atoms.
atoms

Monodentate Ligands

Examples:

[Cu(H2O)2(NH3)2]2+
Bidentate Ligands

Example:ethylenediamine =en
:NH2CH2CH2 :NH2
[Cu(H2O)2(en)]2+

TransitionMetals 19

These are examples of Bi-dentate Ligands

TransitionMetals 20
 Polydentate ligandsbindtothemetal
inmorethan2sites.
Example:ethylenediaminetetraacetic acid
(EDTA)

TransitionMetals 21

Belowarerepresentationsofmetalcomplexeswith
ethylenediamine andEDTAastheligands.

TransitionMetals 22
 EDTA is used to sequester metal ions.

ethylenediaminetetraacetic acid (EDTA)

Applications:
Applications:
Removestracemetalsionsthatcatalyzefooddecomposition

Usedinpoisoncontrol

Usedbylichentoobtain
y
mineralsfromrock.

TransitionMetals 23

ChelatingAgentscanbeused
tosoftenwater

Usedinshampootoremove
Used in shampoo to remove
tracemetalsfromhardwater
(Ca2+ andMg2+):EDTA

Na5P3O10 Used in detergents to remove trace amounts of

dissolved metals:
TransitionMetals 24
 ChelatingAgentsplayimportantrolesinbiological
applications.
applications
Porphine isaflatmolecule
Complexes with this molecule
Complexeswiththismolecule
arecalledporphyrins
CH2

CH CH3

H3C CH2CH3

N N

Mg

N N

CH3
H3C

C20H39OOCH2CH2C

H3COOC O
TransitionMetals 25

ThesearetheImportantChelatingAgentsyouneed
toknow.

Chelate # of Coordination Charge

Sites
Ethylenediamine (en)

P
Porphine
hi
EDTA

Oxalate (C2O42)

Carbonate (CO322)

TransitionMetals 26
 METALCOMPLEXESareverystable.
TheformationreactionshavelargevaluesofK
g f.

Cu(OH2)42+ + 4NH3 Cu(NH3)42+ + 4H2O

Cu2+(aq) + 4NH3 Cu(NH3)42+ + 4H2O

Kf VALUES OF SOME COMPLEXES

[Ag(NH3)2] + 1.7 107

[Cu(NH3)4] 2+ 5 1012
[Cu(CN)4 ] 2 1 1025
[Ag(CN)2 ] 1 1021
[Ag(S2O3)2 ] 3 2.9 1013
TransitionMetals 27

THECHELATEEFFECT:Chelatingligandsformexceptionally
stablemetalcomplexeswhencomparedtorelated
monodentate ligands.
[Ni(H2O)6]2+ + 6 NH3 [Ni(NH3)6]2+ + 6H2O Kf = 4108

[Ni(H2O)6]2+ + 3 en [Ni(en)3]2+ + 6H2O Kf = 21018

[Ni(NH3)6]2+ + 3 en [Ni(en)3]2+ + 6 NH3

What is the expression for the formation constant for this reaction?

TransitionMetals 28
 THECHELATEEFFECT:Chelatingligandsformexceptionally
THECHELATEEFFECT
stablemetalcomplexeswhencomparedtorelated
monodentate
d t t ligands.
li d
This chelate effect is due to :
1) Probability
2) Entropy Effects

Probability Effect:

NH2CH3 H2
Cd+2 N
Cd+2
NH2

NH2CH3

TransitionMetals 29

Sfortheformationofachelateispositive.
1) Cd2+ +4CH
1)Cd 4CH3NH2 [Cd(CH3NH2)4]2+ H =57.3kJ
57 3 kJ

2) Cd2+ +2en [Cd(en)2]2++4H2O H =56.5kJ

Ligand H(kJ) S(J/K) G
1 Methylamine
y 57.3 37.2kJ
CH3NH2
2 56.5 60.7kJ

Why is S so much larger?

[Cd(H2O)4]2+ + 4 CH3NH2 [Cd(CH3NH2)4]2+ + 4H2O

[Cd(H2O)4]2+ + 2 en [Cd(en)2]2+ + 4H2O

TransitionMetals 30