An Introduction to Transition Metal Chemistry

Properties Common to the Transition Elements

1. The free elements conform to the metallic bonding model.

Lattices: close-packed or body-centered cubic
High Thermal & Electrical Conductivities ; Malleable & Ductile.

2. Multi-Oxidation States (Exception: zinc & cadmium)

3. Paramagnetic: Gr St: Unpaired Electrons

NMR, ESR (electron spin resonance), and magnetic susceptibility

4. Electronic Transitions
(of free elements and their compounds & complexes)
Infrared, Visible or ultraviolet region
for the visible cases, of course, colored species are the result.

5. Strong Tendency to Form Complexes:

Cations & neutral atoms: Lewis acids

Complexes (common): 2-6 bases (Ligands)

Oxidation State Tendencies and Their Causes

Oxidation State: Preferences on ionization energy & bond energy

Two perspectives: 1. the maximum (the most oxidized) state & 2. the
preferred (most stable) state

The first half of the 3d series (Sc thru Mn):

Maximum state » “loss” (or, more accurately, the participation in
chemical bonding) of all valence electrons.
Eg: Sc2O3, TiO2, VO2+, CrO3 and MnO4−

Beyond Mn:
Highest state decreased
Eg: FeO42, Co2O3nH2O, NiO2, CuO+ and ZnO.

Decrease from FeVI to ZnII correlates with the number of vacancies

than with the number of occupancies in the valence orbitals of these
elements.
 Maximum Oxidation States: Binary oxides and fluorides (Table 1)

 Cr & Mn:Oxides higher state than fluorides.

 Coordination effect: MnVII requires 7 F & only 4 O

 Most common state is MII (difluorides) of all elements except Sc & Ti

 Electron Configurations of the M2+ cations: [Ar]4s03dx

 A variation of the inert pair effect: s orbital is empty / s orbital w.
nonbonding electron pair

The preferred state:

 The most stable (toward disproportionation or thermal dissociation)
and/or the least reactive
 Highly dependent on ligands
 Metals in high OxSt are hard stabilized by hard bases (e.g. F and O
donors)
 Lower OxSt stabilized by soft bases (S2− and I−)
 Table 1:
 When bonded only to O & F higher states (MIII and/or MIV) / preferred by
early elements; MII is favored later in the series
 Correlates with ionization energies
 Energy to remove 2 & 3 electrons from the 3d elements Fig 1
 Steady increase going across the period in both cases
 Removal of electrons: Sc/44.10 eV ; Mn / 56.75 eV
 (Mn the first element for which the MII state is preferred). Hence, Mn3+ is
destabilized relative to its neutral atom by 12.65 eV (about 1220 kJ/mol)
more than is Sc3+ versus Sc
 The relative destabilization is even greater for Co, Ni, Cu, Zn; (Fe exception
due to pairing energy effect
 Volt-equivalents » oxidation state preferences in aqueous solution
 Table 2: Data for the 3d metals
 Overall trends are similar to those observed for binary fluorides and oxides:
MIII is favored by the early elements, while MII dominates later in the series
 Comparisons of the 3d, 4d, and 5d Elements
 
 Ionization energies 4d elements < 3d congeners
Eg: ∑(IE1:IE3) Tc = 52.08 eV, ~8% < Mn.
 Lower IE’s and reduced steric interactions (longer bonds): Favor high
OxSt’s.
 Most stable fluorides of Nb, Mo, Tc, Ru: NbF 5, MoF6, TcF6, RuF5
(Compare these to the corresponding 3d elements in Table 1)
Ag is exception: AgI state
 5d elements similar to their 4d congeners (TaF5, WF5, etc.)
 Some cases: still higher OxSt’s stabilized (ReF 7, OsF6, lrF4, and PtF4).

o Aqueous Eo known with less certainty for the 4d and 5d elements

o Expected trends hold
o Tendency: decrease OxSt’s across each period & increase OxSt’s down
each group.
Occurrences, Isolation, and Uses of the Free Elements

1. Abundances tend to decrease going down each family

2. Lighter elements normally bonded to O in their natural deposits
The heavier, softer metals generally prefer sulfur
3. OxSt preferences reflected in ores and minerals of these metals
Going across the first transition series, the relative natural abundances follow the order
 
Sc << Ti >> V  Cr < Mn << Fe >> Co < Ni > Cu  Zn

Free elements obtained by chemical reduction

Eg: Titanium (the KroIl Method)
 
TiO2 + 2 Cl2 + 2 C → TiCl4 + 2 CO (1)
 
TiCl4 + 2 Mg (1000o C)→ Ti + 2MgCl2 (2)

TiC14 (volatile, bp = 136°C) easily separated from impurities such as FeC1 3 by

distillation. High-temperature chemical reduction then yields the free metal.
 Iron (the Bessemer Blast Furnace):
 
CaCO3 → CaO + CO2 (3)
 
SiO2 + CaO → CaSiO3 (4)
 
2 C + O2 → 2 CO (5)
 
Fe3O4 + 4 CO → 3 Fe(l) + 4 CO2 (6)
 
Nickel (the Mond Method):
 
2 NiS + 3 O2 → 2 NiO + 2 SO2 (7)
 
NiO + H2 → Ni + H2O (8)
 
Ni + 4 CO 50oC→ Ni(C0)4(g) (9)
 
Ni(CO)4(g)  > 200oC → Ni + 4 CO (10)
 Coordination Compounds and Complex Ions
 
Chemistry of the transition elements:
Metal (Lewis acid—base interactions) with 2 or more donor ligands
coordination compounds or complexes; if charged, they are complex ions
Organometallic Chemistry: metal--metal or metal—nonmetal bonds (not
dative) yet are referred to as coordination compounds or complex ions
General equation complex formation is

Mm+ + n Lx− → [ML]m−nx (11)

 
Enormous number of possibilities:
Variable metal oxidation states
Great variety of ligands available
Different possible coordination numbers
Metal Comlexes: Number of Ligands & Geometric Structure
 Low-Coordinate Geometries
 
Two ligands / central metal: linear or an angular manner ; linear more common
Idealized symmetry (ie, the point group of highest possible order): Dh or Cv

The monovalent cations of Grp 11 form numerous dicoordinate complexes:

CuCl2−, [Ag(NH3)2]+, and [Au(CN)2]− linear

Complexes of HgII (which is isoelectronic with AuI), such Hg(CH3)2 and
Hg(Br)SCN, are known as well
Metal has 10 valence e-
Configurations . . . ns0(n – l)d10 & . . . ns1(n – l)d9 energetically close
Two plausible hybridization schemes:
For s0d10 : electron pairs donated by ligands reside in linear combination of the
ns and npz orbitals → sp hybridization (linear geometry)
sdz2 hybridization also feasible: such hybridization is actually favored (it
removes charge from the region between the metal and ligands (Fig 2)
 Stoichiometry is not predictive of coordination (especially in the solid state)
Eg: FeF2 – CN = 2!?
In crystalline FeF2 & FeF3: CN 6-coordinate octahedral interstices of
fluoride ion sub-lattices

 Complexes metal CN = 3 uncommon

Cu+ as the metal ion
K+[Cu(CN)2]− 1:2 metal:ligand stoichiometry there are two bridging and one
terminal cyanide ligands, with the –Cu–C–N– framework creating a helical
chain Fig 3
 Sterically large ligands → trigonal coordination

Eg: (Me3Si)2N− & (Me3Si)3C− form trigonal complexes with 3d elements

Four bulky groups around metal create steric repulsions sufficient
destabilize the system
M in the plane of the three donor atoms, but in Sc[N(SiMe3)2]3 the scandium
is above the plane (C3v local symmetry.
 Tetrahedral. Square Planar, and Intermediate Geometries8
 
CN = 4 :
 Tetrahedral (for four equivalent ligands, giving local T d symmetry and L–M–L bond
angles of 109.5°)
 Square planar (ideal symmetry D4h, 90o angles)

 Infinite number of possible geometries between these limiting cases; all have
idealized D2d symmetry and bond angles between 90° and 109.5° (Fig 4)

 Intermediate geometries (flattened, squashed, or distorted tetrahedra) less common

than either the tetrahedral or square planar structures
Eg: Complex anions in Cs2[CuX4] (X = Cl and Br), which have X–Cu–X bond angles
between 100° and 103°.

 The geometry (tetracoordinate complex): Steric and Electronic Factors

 Tetrahedron superior / steric

 d electrons determines electronic factors
 Square planar geometry favored by d8 metal ions electrons

Eg: PdII, PtII, and AuIII (Both geometries are common for NiII)

 Steric effect more important for nickel than for its 4d and 5d
congeners because of its smaller size

Ni complexes:difference in stability between the tetrahedral &

square planar geometries is very small

Eg: NiX2(PR)2 (X = Cl− , Br−, and I−; R = alkyl)

 Gradual transition from square planar to tetrahedral geometry

increasing steric bulk (Table 4)

o Several of the intermediate species such as NiBr 2(P2Et)2, can be

produced in either of the two forms.
 Certain ligands dictate (or at least strongly favor) square planar
geometry

 One such donor is terpyridine, a tridentate ligand containing three

aromatic rings (Fig 5a)

 Better examples: tetradentate porphine molecule and its

derivatives, called porphyrins.
 The conjugate  system must remain planar to maintain effective
p overlap

 The result is a natural “hole” for the metal ion, created by the
planar arrangement of donor nitrogens

 The metal may be either in the ligand plane (D4h site or out of the
plane (C4v). Porphyrins are found in many biologically important
compounds (Bioinorganic Chemistry).
Geometric and Optical Isomerism
Stereoisomersspatial arrangement of atoms: geometric and optical isomerism
CN=4 square planar complexes: (cis—trans) isomers Ma2b2
No isomerism is possible for tetrahedral Ma2b2
Historical Importance: existence of two different Pt(NH3)2C12 used by Alfred Werner (father of
coordination chemistry) to prove that (unlike carbon) transition metals often have square planar
geometries
The cis isomer of Pt(NH3)2Cl2 (cis-platin) is an antitumor agent, while the trans isomer is inactive.
 


somerism affected by chelating ligands: bidentate ethylenediamine (en, H2N–CH2–CH2–NH2)
I

substitute for two NH3 ligands to give Pt(en)Cl2

Only cis isomer isolated because en is not long enough for its nitrogens to occupy trans positions
Regardless of geometry complexes: bidentate ligands spanning non-cis coordination sites rare

Tetrahedralgeometry: four different ligands creates an asymmetric metal optical isomerism

Few tetracoordinate metal complexes optically pure enantiomers: rapid racemization at or below
room temperature.
oStereoisomerismthru ligands: via trivalent donor atoms have three different substituents
oBecome asymmetric upon coordination to a metal
oLigands: PH(Me) & N-monomethyl derivative of ethylenediamine, MeNH–CH2–CH2–NH2.
 Trigonal Bipyramidal, Square Pyramidal, and Intermediate Geometries

CN =5
 Uncommon. Produce less stable complexes CN = four or six
 Decomposition:

ML5 → ML4 + L(12)

 
Complexes truly 5-coordinate:
 2 limiting structures plus infinite number of intermediate cases
 Trigonal bipyramid (TBP): D3h
 Square pyramid (SPY): C4v
 Main group atoms 10 valence electrons : TBP electron geometries
 Less clear-cut for metal complexes: energy difference between the TBP and SPY
structures is often small
Eg: 2[Cr(en)3][Ni(CN)5]3H,O

o Solid-state structure contains two different [Ni(CN)5]3− anions, one having a slightly
distorted TBP geometry, and the other, SPY geometry.
 The ideal SPY geometry is essentially never encountered. In square
pyramidal complexes, the metal ion is normally raised out of the
basal plane (typically, by 30–50 pm) toward the axial group:
 
L

M
L L
 
L L

 This changes the SPY bond angles to (calculated) optimum values of

about 104o (axial—basal) and 87o (basal—basal) from the 90o ideal.
Bond angles for the ideal TBP and SPY and for the optimized SPY
geometries are summarized in Fig 7
 TBP and SPY geometries become indistinct thru their
interconversion

Interconversion (facile) → fluxional behavior in solution

Eg: Fe(CO)x(PF3)5–x prepared and exhibit TBP geometry

 Isomerism is possible when x = 1- 4, since there are two non-

equivalent ligand positions (axial and equatorial)

 In solution: all three geometric isomers of Fe(CO)3(PF3)2

PF CO CO
3

CO PF PF
3 3
OC Fe OC Fe OC Fe
CO CO PF 3

PF 3 PF 3 CO
 Octahedral and Distorted Octahedral Complexes
 CN 6: Most common
 Complimentary Geometry: trigonal prism
 Stereoisomerism Octahedrals

 Ma4b2 isomers cis and trans

 Ma3b3 isomers fac (for facial) and mer (for meridional)

Fig 9 , Fig 10 & Table 6

Distortions:

 Trigonal
 Tetragonal (or Jahn-Teller)

Fig 11
 Optical isomerism:
 Common for octahedral complexes having chelating
ligands
Eg: hexadentate EDTA ligand and tris(ethylenediamine)
complexes.

[Co(en)3]3+ belongs to the D3 point group

 Has neither a mirror plane nor an inversion center: optically
active. (Actually, optical activity results from the lack of an
improper axis of rotation. Since S1 =  and S2 = i, the minor
plane—inversion center

(guide identifies nearly all such cases, and so is often used in

place of the more rigorous test.)
 High-Coordinate Geometries

CN ≥ 7 less common

 General rule structural diversity increases with increasing coordination

 Three well-established geometries for CN = 7:

 Pentagonal bipyramid (idealized D5h symmetry)

 Capped octahedron (C3v)
 Capped trigonal prism (C2v)

Fig 12

o Examples for polydentate ligands stabilizing CN ≥ 7

Eg: [Co(crypt)]2+ [Co(SCN)4]2−

 CN = 8 cube, square antiprism, and the dodecahedron (Fig 15)
 (like the trigonal prism and antiprism, common in extended lattices but
rare in discrete complexes)
 Square antiprism Relate to cube like octahedron to trigonal prism—
twisting one face (for the 8-coordinate case, by 45o) generates the
alternative structure.

 Energy differences among these geometries are small, interconversions are

usually facile, fluxionality is common, and the separation of isomers is
often impossible

o Most of the known 8-coordinate complexes have large metal ions (4d, 5d,
lanthanide, or actinide elements) and/or either small or macrocyclic
ligands.
O
 Oxyanions such as NO2−, NO3−, IO3−, and SO42− are often found in
octacoordinate complexes X M
O
 Structural Isomerism
Coordination Isomerism

[Co(NH3)6]3+[Cr(CN)6]3− and [Cr(NH3)6]3+[Co(CN)6] 3− both

have the molecular formula CoCrC6H18N12

Other salts having the same formula: [Co(NH3)5(CN)]2+

[Cr(NH3)(CN)5] 2−

 In two different oxidation states:

Pt2H12C16N4 are the salts [Pt(NH3)4]2+ [PtCI6] 2− [Pt(NH3)4Cl2]2+
[PtCl4] 2−
Ionization and Hydrate Isomerism

Ionization isomerism:
Pt(NH3)3(Br)(NO2)

[(H3N)3PtBr]+NO2− and [(H3N)3PtNO2]+Br−

Two PtII salts: [Pt(NH3)4C12]Br2 and [Pt(NH3)4Br2]Cl2.

Linkage Isomerism

Ambidentate can act as Lewis base thru two or more kinds of

donor atoms
[(H3N)5CoNO2]2+ and [(H3N)5CoONO]2+

nitro & nitrito

Ambidentate: SCN- & SeCN-

2-
SeCN NCSe NCSe

Cd Cd

SeCN SeCN NCSe