Oxidation states

HSAB and geometry

Nomenclature

MST - ANO 1
 Electroneutrality principle *
NH3
NH3 3+
H3N NH3 H3N NH3
3+
Co
Co
H3N NH3
H3N NH3
NH3
NH3

100% ionic model

+NH
3 1
+ /2+
+ NH3
H3N NH3 1
1
/2+
3– /2+
Co NH3
+ + H3N 0
H3N NH3 1 Co
/2+ 1
/2+
+
NH3 H3N NH3
1
/2+ NH3

100% covalent model

50/50 ionic/covalent
MST - ANO 2
 Effects of complexation ***

Alters properties of ligands and metals

• Co(OAc)3 strong oxidizing agent
• [Co(NH3)6]3+ Co is less electron deficient
• Mo(0) strong reducing agent
• Mo(CO)6 air stable; modestly reducing

MST - ANO 3
 Stock nomenclature ***

Use of Roman numerals;

does not imply highly charged ions
• Hexaamminecobalt(III) = [CoIII(NH3)6]3+

• Tetraoxidomanganate(VII) = [MnVIIO4]–

• Hexaaquacobalt(II) = [CoII(H2O)6]2+

MST - ANO 4
 Metal oxidation states **

Ti V Cr Mn Fe Co Ni Cu
0 d5 0 d6 0 d7 0 d8 0 d9 0 d10
1 d4 1 d5 1 d6 1 d8 1 d9 1 d10
2 d2 2 d3 2 d4 2 d5 2 d6 2 d7 2 d8 2 d9
3 d1 3 d2 3 d3 3 d4 3 d5 3 d6 3 d7 3 d8
4 d0 4 d1 4 d2 4 d3 4 d4 4 d5 4 d6
5 d0 5 d1 5 d2 5 d4
6 d0 6 d1 6 d2
7 d0
Formal negative oxidation states are also possible:
Fe–II in K2[Fe(CO)4]; Mn–I in [Mn(CO)5]–
MST - ANO 5
 Electron configurations ***
***
• As metals: often with electrons in s-orbital
– Ni: [Ar] 4s2, 3d8
– Fe: [Ar] 4s2, 3d6
• As complexes: only d-electrons!
– [Ni(CO)4]: Ni(0), [Ar] 3d10
– [Ni(bpy)2]2+: Ni(II), [Ar] 3d8
– [Fe(acac)3]: Fe(III), [Ar] 3d5

MST - ANO 6
 Oxidation states ***
WH6L3  W(VI)
Sometimes ambiguous:
W(CO)6  W(0)
FORMAL oxidation states
WO3  W(VI)
NB: H– very strong reducing agent

S [V(bpy)3]–
V Formally: L2–
S 3
Formal: V(–I)
Spectroscopic:
V(VI) ? d?
V(II), d3 + 3 bpy•–
MST - ANO 7
 Mixed valence

K2[Pt(CN)4](Br)0.3
Partially oxidized Pt

Pt-Pt interactions
Electron conductor!

MST - ANO 8
 Mixed valence CuI + CuII

MST - ANO 9
 Mixed valence “Cu1.5” = CuI + CuII

MST - ANO 10
 Ligands and redox reactions ***

HN NH S S

2+ 2+
Cu Cu

HN NH S S

CH3 CH3

Which of these complexes

is most easily reduced to Cu(I)?
MST - ANO 11
 Stabilization of oxidation states ***

• Cu2+ HSAB: intermediate

geometry: tetragonal,
square planar
• Cu+ HSAB: soft
geometry: tetrahedral

H3C CH3

[Cu(acac)2] O O

cannot be reduced to Cu+

Cu

O O

H3C CH3
MST - ANO 12
 Comparison of redox potentials *
H3C CH3

O O Ered ~ –0.25 V vs NHE

Cu S S
O O
Irreversible to Cu(0) Cu
2+

H3C CH3 S S

CH3 CH3

HN NH E0’ ~ +0.60 V vs NHE

Cu
2+ E0’ ~ –0.15 V vs NHE
Reversible to Cu(I)
HN NH
Reversible to Cu(I) Soft donor atoms
Flexible ligand
MST - ANO 13
 Redox potentials of CuN42+ *

CH2
m
m n R E0’ CuII/CuI vs NHE
R
N N
R
2 1 H –0.20 V
H2C CH2
n Cu
2+ n
3 1 H –0.10 V
N
N
2 2 CH3 +0.10 V
3 2 CH3 +0.28 V

NB: when NR replaced by S: ~ +0.4 to +0.6 V

MST - ANO 14
 Case study: [Mn(phox)3]
R5 R3 R5
H-5’-NO2phox H NO2
R3
O H-3’,5’-dClphox Cl Cl
OH N H-5’-Clphox H Cl
Hphox H H
N
H-5’-Mephox H CH3
O N
Mn H-3’-Mephox CH3 H
O O [MnIII(L)3] H-5’-MeOphox H OCH3
N

??  [MnII(L)3]–  [MnIII(L)3]  [MnIV(L)3]+  [MnV(L)3]2+ ?

MST - ANO 15
 Redox: [MnII]–  [MnIII]  [MnIV]+
 
complex MnIII/MnII MnIII/MnIV
[Mn(L)3] E½ Ep E½ Ep
5’-NO2phox +0.12 80 +0.87 65 [Mn(5’-NO2phox)3]
3’,5’-dClphox –0.07 100 +0.75 65 [Mn(5’-MeOphox)3]
5’-Clphox –0.26 120 +0.60 75
phox –0.42 260 +0.48 85
5’-Mephox –0.45 180 +0.42 60
3’-Mephox –0.52 230 +0.40 90
5’-MeOphox –0.49 220 +0.41 90
E/V (vs. Ag/AgCl)

1.50 1.00 0.50 0.00 -0.50 -1.00

MST - ANO 16
 Metalloenzymes / metalloproteins

Function and oxidation state

are correlated to

Coordinating amino acid groups

and
Geometry constraints

MST - ANO 17
 Question on blue copper proteins

Amicyanin is a protein containing one copper center.

It is involved in electron transfer from methylamine
dehydrogenase (MADH) to the heme of cytochrome c.
Which type of coordination sphere do you expect:
(a) CuS4
(b) CuN2S2
(c) CuO2S2
(d) CuN2O2
(e) CuO4

MST - ANO 18
 Active site in amicyanine
Met99 Cys93
• in plane His-His-Cys
– (Cu-S=2.1 Å, Cu-N=2.0 Å)
• axial Met site His96 His54
– (Cu-S=2.7-3.2 Å)
• out-of-plane distance of Cu < 0.5 Å
• copper center moves from the trigonal plane toward the
methionine donor
• Cu-S(Met) distance is approximately inversely correlated to
the Cu-S(Cys) distance
• hydrophobic environment contributes to stabilizing CuI

MST - ANO 19
 Entasis
"energization due to a misfit between ligands and metal ions"
or
geometrically constraining a metal coordination sphere to stabilize
or destabilize simultaneously different oxidation states

Example:
• CuI likes tetrahedral geometry
• CuII prefers square-planar or square-pyramidal environment
• N2S2 trigonal pyramidal binding site in amicyanin forces similar
coordination geometries in both oxidation states
• some flexibility for the motion of Cu upon ET results in
improved ET rates

MST - ANO P. Comba, Coord. Chem. Rev. 2000, 200-202, 217-245 20

 Entasis in amicyanin
Oxidized form amicyanin (CuII): [Cu(OH2)6]2+ in water:
• extremely intense absorption • weak d-d absorption band
band (λmax ~ 600 nm, εmax ~ (λmax ~ 600 nm, εmax < 100
5000 M-1.cm-1), d-d in the M-1.cm-1)
low energy tail
• high redox potential 200-500 • redox potential 150 mV vs
mV vs SHE SHE
• high electron transfer rates: • low electron transfer rates:
103 to 107 M-1.s-1 5×10-7 M-1.s-1
• low reorganization energy • high reorganization energy
upon electron transfer upon electron transfer

MST - ANO P. Comba, Coord. Chem. Rev. 2000, 200-202, 217-245 21

 Nomenclature of complexes ***

• Ligand names precede metal

– Ligands in alphabetical order
– Neutral: e.g. bipyridine, acetone, imidazole
– Negative ends with -o: chlorido, hydroxido
– Negative organic with -yl: methyl, phenyl, acetyl
– Positive ends with –ium
– Special: ammine (NH3); carbonyl (CO); aqua (H2O)
• Numeric additions:
– di(bi)/tri/tetra
– For more complicated names: bis/tris/tetrakis
• Info about isomer: cis/trans; mer/fac; /

MST - ANO 22
 Nomenclature of complexes ***

• If ambiguous: indicate donor atom after name ligand

(thiocyanato-S);
also done with prefix  (thiocyanato-N)
• Indicate bridging ligands with prefix 
• Organic groups as usual: methyl, phenyl
• Cations before, anions and solvates after complex name
• Complex name ends with –ate when anionic (e.g.
permanganate for MnO4)
• Add Stock number when necessary (CTO 4)

MST - ANO 23
 Nomenclature and terminology **

Correct Unusual or incorrect

kDa; Da; MDa Kd, D, K, MD

Sulfur, sulfate Sulphur, sulphate
Copper(I) Cuprous
Copper(II) Cupric [Copper(III)]?
Iron(II) Ferrous
Iron(III) Ferric
Coordinated Liganded; ligated
Aqua Aquo
Mg2+ Mg++ Mg+2
O2•– O2–• •–O2
S2– S= S–2
MST - ANO 24
 [RuCp(tappe)]
(5-cyclopentadienyl)-

{1-(bis(o-methoxyphenyl)phosphanyl-P)-
2-(o-methoxyphenyl(o-phenolato-O)-phosphanyl-P)
ethane}ruthenium(II)

MST - ANO 25
 Examples nomenclature

Na[Mn(acac)3] Sodium tris(acetylacetonato) manganate(II)

[Fe(acac)3] tris(acetylacetonato)iron

K3[Fe(CN)6] Tripotassium hexacyanidoferrate

[Cr(H2O)6]Cl3 Hexaaquachromium trichloride

[Cr(H2O)4Cl2]Cl•2H2O Tetraaquadichloridochromium(III) chloride

dihydrate

MST - ANO 26
 Examples and exercise
1 dichloridobis(dimethylsulfoxide)zinc

2 Tripotassium pentakis(trichloridostannato)platinate

3 Dicesium hexachloridoantimonate(III,V)

4 bromidochloridofluoridoiodidolead

5 pentaammine(triiodido)thallium and triamminetriiodidothallium

6 Potassium tetrachloridoiodate(III)

7 hexakis(acetonitrile)nickel bis(tetrachloridoaluminate)

MST - ANO 27
 Examples and exercise
8 fac-trichlorido(diethylenetriamine)rhodium

9 methyltrioxidorhenium

10 cis-diamminechlorido(pyridine)platinum(II) chloride

11 cis-diammine(chloropyridine)iodidoplatinum(II) nitrate

12 di-µ-chlorido-{bis(tetraammineruthenium(II)}-
bis(hexafluoridophosphate)
13 bis(cyclopentadienyl)dimethyltitanium

14 tetrakis(4-methylpyridine)bis(thiocyanato-N) nickel

MST - ANO 28
 Summary keywords

• Electroneutrality principle, ionic model, covalent model

• Complexation alters properties of ligands and metals!
• Stock notation of oxidation states
• Mixed valence compounds
• Stabilisation of oxidation states
– HSAB and geometry effects
• Nomenclature

MST - ANO 29
 Assignment

• Study H6, § 6.1 – 6.6

– p 188 - 197

MST - ANO 30