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Cu: plumbing
Fe: in steel
Cr: in automobile parts
Au, Ag: jewelry
W: light bulb filament
Ti: bicycle
Pt: auto catalytic converters
Zr: nuclear-reactor liners
Nitrinol (Ni and Ti used in stents)
And many more
The transition elements (d block) and inner transition elements (f block) in the
periodic table
1
Example
Writing Electron Configurations of Transition Metal Atoms and Ions
Write condensed electron configurations for the following: (a) Zr; (b) V3+ (c) Mo3+.
(Assume that elements in higher periods behave like those in Period 4.)
Note that the general configuration is [noble gas] ns2(n - 1)dx. Recall that in ions the ns
electrons are lost first.
2
Horizontal trends in key atomic properties of the Period 4 elements
Atomic size decreases overall across a period. The d electrons fill inner orbitals,
so they shield outer electrons from the increasing nuclear charge very efficiently
and the outer 4s electrons are not pulled closer.
Electronegativity usually increases across a period but the transition metals
exhibit a relatively small change in electronegativity. Metal in higher oxidation
state is more positive has stronger pull on electron is more electronegative
IE1 increase relatively little because the inner 3d electrons shield efficiently and
the outer 4s electron experiences only a slightly higher effective nuclear charge.
3
Trends Within a Group (relative to main-group elements)
Atomic Size
Increases as expected, from Period 4 to 5. No increase from Period 5 to 6
Lanthanides with buried 4f sublevel orbitals appear between the 4d (period 5) and 5d
(period 6) series
An element in Period 6 is separated from the one above it in Period 5 by 32 electrons
(ten 4d, six 5p, two 6s, and fourteen 4f). The extra shrinking that results from the
increased nuclear charge due to the addition of the fourteen 4f electrons is called the:
Lanthanide Contraction
4
No change from period 5 to period 6, since the change in volume is small and Zeff
increases (f orbital electrons).
Transition metals exhibit more covalent bonding and attract electrons more strongly
than main-group metals
The EN values in the heavy metals exceed those of most metalloids, forming salt-like
compounds, such as CsAu and the Au- ion
Ionization Energy
Main-group elements increase in size down a group, decreasing the 1st ionization
energy, making it relatively easier to remove the outer electrons
The relatively small increase in size of transition metals, combined with the relatively
large increase in nuclear charge (Zeff), results in a general increase in the first ionization
energy down a group
Density
5
Exhibit more than one
Ionic bonding is more prevalent for the lower oxidation states and covalent
bonding is more prevalent for the higher oxidation states.
At room temperature TiCl2 is an ionic solid and TiCl4 is a molecular liquid
In high oxidation states atoms have higher charge densities polarize electron
clouds of non-metals covalent bonding
The oxides become less basic as the oxidation state increases
TiO is a weak base in water and TiO2 is amphoteric.
Most main group ionic compounds are colorless because the metal ion has a
filled outer level;
On the contrary,
Electrons in particular filled d-sublevels can absorb visible wavelengths and
move to slightly higher energy d-orbitals. Therefore, many transition metal
compounds have striking colors. Exceptions occur when d orbitals are empty
or filled. Zn2+: [Ar] 3d10 and Sc3+ or Ti4+ [Ar] 3d0
These are species consisting of a central metal cation (transition metal or main group
metal) that is bonded to molecules and or anions called ligands. In order to maintain
neutrality in the coordination compound, the complex ion is typically associated with
other ions, called counterions.
Therefore,
6
Metals ions are Lewis acids, because they accept electrons from Lewis bases. When
metal cations combine with Lewis bases, the resulting species is called a complex ion,
and the base is called a ligand.
1s0 1s 11s 11s 1
+
H H H H
Hydrogen ion has a vacant 1s orbital.
H +
H Nitrogen has a full sp 3 orbital.
+ A co-ordinate covalent bond is formed
H N: + H H N H N when nitrogen donates its lone e - pair
H H to hydrogen's empty 1s orbital.
sp3 orbitals
ammonia
ammonium ion
2pz
sp2 orbitals
H F H F
Boron has a vacant 2p z orbital.
H N: + B F H N B F B Nitrogen has a full sp 3 orbital.
H A co-ordinate covalent bond is formed
F H F
ammonia N when nitrogen donates its lone e - pair
to boron's empty 2p z orbital.
sp3 orbitals
Ammonia is the Lewis base (electron donor). H+ and BF3 are Lewis acids (electron
acceptors).
Similarly, transition metals and their cations are Lewis acids. They have vacant orbitals
that can accept electron pairs from donor atoms (Lewis bases) forming coordination
compounds or complexes. Some examples are shown in the following table.
Lewis bases (anions or molecules) bonded to the central Lewis acid are called ligands
(Latin = tie or bind). Charged coordination complexes also have counter ions
associated with them to satisfy electroneutrality. For example, in [Ag(NH3)2]+NO3-, a
nitrate anion is the counter ion. Counter ions are ionically bonded. When dissolved in
water, the NO3- ion separates from the complex, but the two NH3 ligands remain firmly
bound to the Ag+ ion by covalent bonds.
7
Components of a Coordination Compound
When solid complex dissolves in water, the complex ion and the counter ions separate,
but ligands remain bound to central atom
Coordination Number (CN) - the number of ligand atoms that are bonded directly to
the central metal ion. The coordination number is specific for a given metal ion in a
particular oxidation state and compound (6 is the most common, 2 and 4 are often used.)
Geometry - the geometry (shape) of a complex ion depends on the coordination number
and nature of the metal ion. See table below
Donor 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 bond.
phthalocyaine blue is a Cu complex dye used for blue jeans and ink
complexing agents are used for water softening (Ca, Mg, Fe removal with EDTA)
8
an antidote for some metal poisoning (BAL) forms complexes with As, Hg, and Cr.
Fe-carbonyls are anti-knock gasoline additives
2 sp (BeH2) sp [Ag(NH3)2]+
linear [Cu(CN)2]-
4 sp3 (CH4) sp3 [Zn(CN)4]-2
109.5 [Cd(NH3)4]+2
[FeCl4]-
[Co(Br)4]-2
tetrahedral
4 90
sp3d2 (XeF4) dsp2 [Pd(CO)4]+2
90
[Pt(NH3)2Cl2]
[Ni(CN)4]-2
square planar
5
a
sp3d (PCl5) d3sp or dsp3 [CuCl5]-3
90
[Fe(CO)5]
e or sp3d
e [Mn(CO)4NO]
120
[Ni(CN)5]-3
triangular bipyramidal
e e = equitorial position
a a = axial position
6 sp3d2 (SF6) d2sp3 or sp3d2 [PtCl6]-2
[Co(NH3)6]+3
90
[Fe(OH2)6]+2
90 [Fe(CN)6]-4
[MoF6]-
[CoF6]-3
octahedral
[Ni(H2O)6]+2
[Mn(CN)6]-4
9
Typical CN for some common ions
M+ CN M2+ CN M3+ CN
+ + 2+ 2+ 2+ 2+ 2+ 3+ 3+ 3+
Cu , Au 2,4 Co ,Ni , Cu ,Zn Mn 4,6 Sc , Cr , Co 6
Ag+ 2 Fe2+ 6 Au3+ 4
Example
a) What is the systematic name of Na3[AlF6]?
11
b) What is the systematic name of [Co(en)2Cl2]NO3?
dichlorobis(ethylenediamine)cobalt(III) nitrate
Chelates
Notice how the ligand grabs the metal from two sides like a claw
12
Coordination Complexes
Porphine heme
Coordination isomers occur when the composition of the complex ion changes but not
that of the compound
Linkage isomers occur when the composition of the complex ions remains the same but
the attachment of the ligand donor atom changes
[Co(NH3)5(NO2]Cl2 , [Co(NH3)5(ONO]Cl2
13
Geometric isomers (also called cis-trans and sometimes diastereomers) occur when
atoms or groups of atoms are arranged differently in space relative to the central metal
ion.
Beyond cis and trans isomers: facial & meridian isomers and enantiomers
CoCl3 3NH3
Cl Cl
H3N Co Cl H3N Co Cl
H3N Cl H3 N NH3
NH3 Cl
facial (fac) meridian (mer)
Optical isomers (also called enantiomers) occur when a molecule and its mirror image
cannot be superimposed. Optical isomers have distinct physical properties like other
types of isomers, with one exception the direction in which they rotate the plane of
polarized light.
14
Enantiomers: non superimposable mirror images
Enantiomers
NH3 NH3
H3N Co Cl Cl Co NH3
H2O Cl Cl H2O
H2O H2O
15
Chirality: absence of a plane of symmetry, possible enantiomers
Which are enantiomers (non-superimposable mirror images) and which are identical
(superimposable mirror images)?
16
- Rotating structure I in the cis compound gives structure III, which is not the same as
structure II, its mirror image, Image I & Image III are optical isomers
- Rotating structure I in the trans compound gives structure III,which is the same as
structure II, its mirror image, The trans compound does not have any mirror images
17
Determining the Type of Stereoisomerism
PROBLEM: Draw all stereoisomers for each of the following and state the type
of isomerism:
:
(b) [Cr(en)3]3+ (en = H2NCH2CH2 NH2)
:
(a) [Pt(NH3)2Br2]
PLAN: Determine the geometry around each metal ion and the nature of
the ligands. Place the ligands in as many different positions as
possible. Look for cis-trans and optical isomers.
SOLUTION: (a) Pt(II) forms a square planar complex and there are two pair
of monodentate ligands - NH3 and Br.
18
Application of VB Theory to Complex Ions
2-Coordinate Compounds:
Linear sp hybridized transition metal complexes:
a) Consider [Ag(NH3)2]+ Ag = 5s1 4d10 Ag+ = 5s0 4d10
4d 5s 5p sp 5p
sp
+ +
Ag [Ag(NH3)2]
hybridized
:NH3 :NH3
5s 5p sp3
4d sp3
+2 +2
Cd [Cd(NH3)4]
hybridized
tetrahedral
.. .. .. ..
NH3 NH3 NH3 NH3
19
Note that all 4-coordinate complexes of a s0 d10 ion are sp3 hybridized and tetrahedral,
e.g.,
+2
4-coordinate complexes of Group 2B M ions: Zn+2, Cd+2, Hg+2
+1
4-coordinate complexes of Group 1B M ions: Cu+1, Ag+1, Au+1
In four coordinate complexes of s0d8 ions (Ni+2, Pd+2, Pt+2), two molecular geometries
are encountered, tetrahedral (sp3) and square planar (dsp2).
Consider [NiCl4]-2 Ni = 4s2 3d8 Ni+2 = 4s0 3d8
sp3
3d 4s 4p hybridized sp3
3d
+2 -2
Ni [NiCl4]
tetrahedral
3d 4s 4p
square - - -
CN CN- CN CN
planar
In dsp2 hybridization, one d-orbital is empty and receives an electron pair from the
ligand. Donor atoms are situated on the x and y -axes of the square planar structure.
Note that in the term 'dsp2', 'd' precedes 'sp2' indicating that the d-orbital used in
hybridization comes from a lower (inner) shell than the 's' and 'p' orbitals. This is called
inner shell hybridization. In the previous unit on bonding, we saw terms such as
'sp3d'. In this case, where 'd' follows 'sp3', the d-orbital is from the highest energy level,
e.g., recall that PCl5 has sp3d hybridization (triangular bipyramidal geometry). This is
called outer shell hybridization.
20
Six Coordinate Complexes (Octahedral):
Six ligand donor atoms in an octahedral complex are located at the corners of an
octahedron. Valence bond postulates that the orbitals best shaped and best oriented to
receive electron pairs from these directions are the dx2-y2 and dz2 orbitals (directed on the
x, y, and z-axes).
Consider [Fe(CN)6]-3 Fe = 4s2 3d6 Fe+3 = 4s0 3d5
3d 4s 4p
+3
Fe
d2sp3 d2sp3
3d 4s 4p hybridized 3d
-3
+3 [Fe(CN)6]
Fe
octahedral
- - - -
CN CN- CN CN- CN CN
CN- is a strong field donor, forcing inner 3d electrons into a lower spin state and
hybridizing inner 3d orbitals, i.e., d2sp3 (inner shell hybridization). H2O, a weaker field
donor, is not able to bring about inner shell hybridization and the resulting hybridization
is thus sp3d2. Both d2sp3 and sp3d2 complexes are octahedral.
Consider [Fe(H2O)6]+3 Fe = 4s2 3d6 Fe+3 = 4s0 3d5
3d 4s 4p 4d sp 3d2 3d sp 3d2 4d
hybridized
+3
Fe
octahedral
+3
[Fe(H2O)6]
H2O H2O H2O H2O H2O H2O
Metal ions in which two d-orbitals are vacant will form inner shell hybridized d2sp3
octahedral complexes.
Metal ions in which two d-orbitals are not vacant will form either outer shell sp3d2
hybridized octahedral complexes (with weak ligands) or inner shell d2sp3 hybridized
octahedral complexes with strong ligands (If half-filled d-orbitals are present a low spin
state can be forced).
Study the following examples and note where inner and outer shell hybridization occur
and why.
x = an electron pair donated from a ligand
x
d6 Co+3
3d 4s 4p 4d
[Co(NH3)6] +3 x x x x x x strong ligand
x x x x x x
d2sp 3
3d 4s 4p 4d
-3 x x x x x x
[CoF6] x x x x x x weak ligand
21
sp 3d2
d5 Mn+2
3d 4s 4p 4d
-4 x x x x x x
[Mn(CN)6] x x x x x x
d2sp 3
d8 Ni+2
3d 4s 4p 4d
+2 x x x x x x
[Ni(H2O)6] x x x x x x
sp 3d2
+3
d3 Cr
3d 4s 4p 4d
[Cr(NH3)6]
+3 x x x x x x
x x x x x x
d2sp 3
What is color?
22
Valence Bond Theory in Coordination Compounds: An Overview
Ligands (Lewis base) form coordinate covalent bonds with metal center (Lewis
acid)
Relationship between hybridization, geometry, and magnetism
Inadequate explanation for colors of complex ions
e.g., [Cr(H2O)6]3+, [Cr(H2O)4Cl2]+
Overview of d orbitals
23
Splitting of d-orbital energies by an octahedral field of ligands
24
The color of [Ti(H2O)6]3+
[V(H2O)6]3+
[V(H2O)6]2+
For a given ligand, the color depends on the oxidation state of the metal ion.
For a given metal ion, the color depends on the ligand.
25
Ranking Crystal Field Splitting Energies for
Complex Ions of a Given Metal
SOLUTION: The ligand field strength is CN- > NH3 > H2O, so the relative
size of and energy of light absorbed is
26
Identifying Complex Ions as High Spin or Low Spin
PROBLEM: Iron (II) forms an essential complex in hemoglobin. For each of the
2+ 4-
two octahedral complex ions [Fe(H2O)6] and [Fe(CN)6] , draw an
orbital splitting diagram, predict the number of unpaired electrons,
and identify the ion as low or high spin.
2+
PLAN: The electron configuration of Fe gives us information that the iron
has 6d electrons. The two ligands have different field strengths.
Draw the orbital box diagrams, splitting the d orbitals into eg and
t2g. Add the electrons noting that a weak-field ligand gives the
maximum number of unpaired electrons and a high-spin complex
and vice-versa.
SOLUTION: [Fe(CN)6]4-
PE [Fe(H2O)6]2+ --
4 unpaired e eg
(high spin)
eg no unpaired e
--
(low spin)
t2g
t2g
27
Organometallic compounds: and bonded compounds
Bonding in carbonyls
M + C O: M C O:
-overlap
M + C O: M C O
-overlap
28
Bonding in alkenes
C C
- overlap
M + M
C C
C C
Back-bonding
M + M
C C
29