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CHEM 1101 | Transition Metals

Introduction

• A TM is an element that forms a compound in which the metal has a partially filled d-
subshell of electrons

• TM on the LHS have a low electron count and are electron poor / deficient (e.g.
Group 4: Ti, Zr, Hf). They are expected to lose electrons to obtain noble gas
configuration (e.g. TiO2, where Ti4+ has [Ar])

• TM on the RHS have a high electron count and are electron rich (e.g. Group 10: Ni,
Pd, Pt). They are likely to form complexes in which they gain electrons to obtain
noble gas configuration (e.g. Fe(CO)5 or Ni(CO)4)

• TM show extremely diverse chemistry and are ‘stable’ in a variety of OS, they form
highly coloured compounds and complexes and also form magnetic compounds

Bulk Usage of TM

Metal Use
Fe Steel
Cu Piping, electrical wire, alloys (e.g. brass)
Cr Metal plating, alloys, pigments
Ni Steel, alloys, metal plating
W Light bulb filaments, superalloys
Ag Precious goods
Au Currency / coinage, electrical, jewellery

Biochemistry

• TM are fundamental in a variety of life processes

• The human body requires Fe and trace amounts of Co, Mn, Cu (e.g. haemoglobin
and vitamin B12)

Haemoglobin / Myoglobin

• Haemoglobin is an iron containing protein found in mammalian RBC and is used for
transporting oxygen molecules around the body

• Myoglobin is similar but transports oxygen from the blood to the muscles

• In haemoglobin, Fe(II) + O2 ⇌ Fe(II)–O2 complex

• Reversible with O2 but slowly reversible with CO and irreversible with CN–

• Protein prevents [O] of Fe(II) to Fe(III)

Vitamin B12
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• Co containing compound and it is the only known biological organometallic

compound with a metal Co–C bond (6 ligands)

TM Catalysts

Zieglar-Natta catalysis

• Used to make polymeric hydrocarbons like linear polyethylene (HDPE: high density
polyethylene)

• Isotactic polymerisation C2H4 → –(–C2H4–)n–

• Free radical methods produce branched chains

• Catalyst / co-catalyst like TiCl4 usually in the presence of Al(C2H5)3 but not good for
making PVC –(–C2H3Cl–)n–

Fischer-Tropsch Process

• Used to make aliphatic compounds by reducing CO with H2 at high temperature

(400oC)

• CO + H2 → –CH2– and –CH2OH

• Catalysis is historically Fe and CO based but more specific ones are Ru based

• Products include LPG, petrol and diesel

Wilkinson’s catalyst

• Used to selectively hydrogenate terminal methylene groups with H2 gas at normal

pressure

• Homogeneous catalyst: RhCl(PPh)3

• R,R’C=CH2 + H2 → R,R’CHCH3

Applications

• Zirconia ZrO2 is used as a catalytic converter in most car exhausts and also in cubic
zirconia synthetic gemstones (cheap diamond substitute, coloured by doping with TM
oxides or rare earth oxides)

• High temperature superconductors (e.g. La2–xSrxCuO4, Ba2YCu3O7–x)

• CMR (colossal magnetoresistance) materials like (La,Ca)MnO3 where electrical

resistance is linked to magnetic properties

Electronic Configuration
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• For 1st row TM, 4s subshell fills first before 3d subshell. 4s becomes energetically
more favourable than 4p subshell

• Half filled and fully filled d subshells (d5 and d10) are energetically more favourable
than s subshell due to ‘exchange’ energy

• Hence, Cr: [Ar]3d54s1 and Cu: [Ar]3d104s1

• However, for oxidised TM atoms, the d subshell is energetically more favourable than
the higher no s subshell

• For electron counting, ALWAYS assume no electrons in the higher s subshell and all
outer electrons are in the d subshell (i.e. Sc: 3d3 → Sc+: 3d2, Cr: 3d6 → Cr3+: 3d3)

• A ligand is a neutral or anionic group that binds directly to the TM

• Neutral ligands include H2O, NH3, NR3, CO, PR3 (e.g. PPh3)

• Anionic ligands include F–, Cl–, Br–, I–, CN–, NH2–, SCN–, NCS–, O2– (oxo), NH2–
(imido), N3– (nitrido)

• A complex is a species formed by the coordinating ligands with the metal centre (e.g.
[Fe(CN)6]4–

Determining OS

• The chemistry of TM is dominated by the no of d electrons which is directly related to

OS

• Determined by working out the charge on the ligands and taking into account the
effect of the charge on the overall complex

OS Rules

• For p block elements, OS generally changes by 2

HCl HOCl [HClO2] HClO3 HClO4

I– I+ III+ V+ VII+
PH3 [H3PO] H3PO2 H3PO3 H3PO4
III– I– I+ III+ V+

• For d block elements, they have variable OS and do not follow any rule

• D electron count: subtract the OS of TM from its Group no in the Periodic table

• Example: Co(II) in [Co(H2O)6]2+ (pink)

Co (Group 9) → No of d electrons = 9 – 2 = 7 [Ar]3d7

• Mn(VI) in K2MnO4 (green) Mn: (Group 7) No of d electrons = 7 – 6 = 1 [Ar]3d1

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• OS is usually positive but there are exceptions

(e.g. [V(CO)4]– anion has V(–I) so V (Group 5) → No of d electrons = 5 –(–1) = 6
[Ar]3d6)

Ligands

• All ligands donate electrons to the metal (do not include these electrons when
working out the d electron count of the metal)

• By convention, neutral ligands (L) and anionic ligands (X)

• Monodentate refers to a ligand that has one atom that binds to the TM
e.g. X (F–, Cl–, Br–, I–, CN–, NCS–, NO2–, OH–)
L (H2O, NH3, CO, CH3OH, NH2R, PPh3)

• Each ligand donates 1 pair of electrons to the TM

• Polydentate refers to a ligand that contains 2 or more atoms that simultaneously

binds with a pair of electrons to the TM (e.g. bidentate, tridentate etc.)

• ‘Chelating’ ligands are ligands that bond with more than one atom to the metal centre
(where the first binding is slow but subsequent bindings become faster)

Bidentate Ligands

Type Examples
L2 Glyme CH3–O–CH2–CH2–O–CH3

Oxalate anion / ox: (COO)22–,

Ethylene diamine / en H2N–CH2–CH2–NH2 (note single,

not double bond despite name)
LX Acetylacetonate / acac [CH3–CO–CH–CO–CH3] –

X2 Sulphate SO42–
Carbonate CO32– (O are adjacent to each other)

These are weak ligands which may bridge Mn+

Tridentate Ligands
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• Type L3: Terpyridyl / terpy: C5H4N–C5H3N–C5H4N

Tetradentate Ligands

• Various rings e.g. in haem / corrin

Hexadentate Ligands

• Type L6: 18-crown-6-ether which complexes alkali metals

• Type L2X4: ethylene diamine tetraacetate (EDTA)

(–OCOCH2)2NCH2CH2N(CH2COO–)2 used to sequester metal cations in aqueous
solution (especially +2 species) and manufactured in bulk as sodium salt

Inner vs Outer Sphere

• Inner sphere: ligands that bond directly to the metal

• Outer sphere: groups that are not directly attached to the metal centre but form part
of the complex

• Notation: analytical vs structural chemistry, solution vs solid state

(e.g. FeSO4.7H2O = [Fe(H2O)6](SO4)(H2O) )

• Ligand strength: CN– > NH3 > H2O > X– > H3O+ (if H3O+ binds to Mn+, charge repulsion)

Coordination Number
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• CN refers to the no of atoms directly bonded to the metal (includes only inner sphere
ligands)

• The no and type of ligand in a TM complex play a very important role with regards to
its physical properties like UV / visible spectrum (colour) and magnetic behaviour

• Low CN (1 or 2) are extremely rare in solid state, but may be found in the gas phase

• Example: VO+ and VO2+ (CN=1), but in practice, these will be solvated in aqueous
solution

CN = 2

• E.g. [NH3–Ag–NH3]+, [Cl–Ag–Cl]–, Hg(CN)2, CuCN, AgCN, AuCN

• For CuCN, it is made up of linear chains in [CN–Cu–CN–Cu–]n with C at one end

and N at the other

• The complexes often react further to give higher coordination no complexes

• E.g. [Ag(NH3)2]+ + 2NH3 → [Ag(NH3)4]+

• Hg(CN)2 + 2CN– → [Hg(CN)4]2–

CN = 3

• Exceedingly rare

• 2 geometries: Planar (e.g. [HgI3]–, [Cu(SPMe)3]+, Pt(PPh3)3) or pyramidal (e.g.

[SnCl3]–)

• However, beware of judging purely based on stoichiometry

• Example: Pt with d8 configuration prefers to be square planar (as in PtCl2PR3: square

planar and bridged)

• Also, AlCl3 is a dimer Al2Cl6 (tetrahedral [AlCl4] double bridged moiety)

CN = 4 (important)

• Very common

• 2 geometries: tetrahedral (‘normal’, e.g. [CoCl4]2– and square planar (common for
d8 metal ions: Ni2+, Pd2+, Pt2+, Au3+, Rh+, Ir+) e.g. [PtCl4]2–, [AuCl4]–

• For big ligands, complexes tend to be tetrahedral. For small ligands, complexes tend
to be square planar

CN = 5
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• Much less common

• 2 geometries: trigonal bipyramidal or square pyramidal

• E.g. Trigonal bipyramidal – Cu(II) anion in [CuCl5]3– where axial is shorter than
equatorial due to [Ar]3d9

• Square pyramidal – [Ni(CN)5]3– where the Ni is not in the square plane

CN = 6 (important)

• Most common CN

• Featured by high charge e.g. Cr3+ / Fe3+

• 2 geometries: trigonal prismatic (exception) or octahedral (normal)

• Note: show 3D geometry about central atom (hashed and wedged lines)

CN = 7 →

• Higher CN occur for 2nd and 3rd row TM due to increasing size

• CN = 7 is exceedingly rare

• 3 geometries: pentagonal bipyramidal, capped octahedral, capped trigonal prismatic

• Due to low activation energy barrier between the geometries, interconversion occurs
easily

Isomerism

Cobalt Complexes
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• Examples of Co(III) salts: CoCl3.6NH3 (yellow), CoCl3.5NH3 (purple), CoCl3.4NH3

(green), CoCl3.4NH3 (violet)

• Chloride salts give different reactions with excess aqueous silver nitrate

Cl– (aq) + AgNO3(aq) → AgCl (s) + NO3–(aq)

• Cobaltic salts are 6 coordinate (primary valence)

• Reacts with AgNO3 (inner and outer sphere)

CoCl3.6NH3 (yellow) [Co(NH3)6]3+(Cl–)3

CoCl3.5NH3 (purple) [Co(NH3)5Cl]2+(Cl–)2
CoCl3.4NH3 (green) [Co(NH3)4Cl2]+Cl–
CoCl3.4NH3 (violet) [Co(NH3)4Cl2]+Cl–

Geometric Isomerism

• Geometric isomerism ina TM complex occurs for complexes of the type ML4X2

• E.g. [Co(NH3)4Cl2]+

• Cis when X ligands are adjacent and trans when X ligands are opposite

• Similar isomerism in square planar d8 TM (e.g. Pt(NH3)2Cl2)

• Geometric isomerism in a TM complex also occurs for complexes of the type ML3X3

• 2 types: Facial (fac) where X groups lie on the triangular plane of the octahedral and
Meridonal (mer) where X groups are in the horizontal plane (including the central TM)
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Linkage Isomerism

• Formed when a ligand can bond through 2 different donor atoms

• Ambidentate ligands which bind to the metal in more than one way

• E.g. NCS– / SCN– which can bind via N (hard centre) or S (soft centre),
NO2– (nitro) / ONO– (nitrito) which can bind via N or O

• Order indicates binding order (i.e. NCS– : M–N=C=S; SCN–: M–S–C≡ N

Ionisation Isomerism

• Different anion / ligand bonded to the central metal, but same chemical formula

• Related to geometric isomerism but relates to inner and outer sphere of a complex

Example CoCl2NO2.4NH3

• [Co(NH3)4Cl2]+ NO2– (both cis and trans forms) 2

• [Co(NH3)4ClNO2]+ Cl– (both cis and trans forms) + linkage isomerism for NO2– / ONO–
2x2

• Total = 6 isomers

Optical Isomerism
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• Compounds which are non-superimposable mirror images

• Remember to draw in hashed and wedged bonds and draw mirror line to obtain the
other enantiomer

• E.g. [Co(OH)6{Co(NH3)4}3]6+ contains 3 bidentate cations [Co(NH3)4]3+ that bridge the

O atoms in the central octahedral complex [Co(OH)6]3–

• The main form of optical isomerism in TM chemistry is observed for octahedral

complexes that contain a chelating bidentate ligand such as en or ox

• Occurs when the symmetry of the complex has only proper rotations (e.g. Cn or Dn)

• No internal mirror planes (or rotation-reflection / rotary inversion)