Ch 19.

d-Block Metals

Hvap (in kJ/mol) for Metals

Tm
Ba
W
Au

725C
3410C
1064C

Tm across TM

Quick Review of Redox Rxns

To balance a half-reaction:
1.
2.
3.
4.

Identify and balance redox atoms

Add e as needed
Add H+ or OH- to balance charge
Add H2O as needed

Ex:
Balance HMnO4 Mn2+ in acidic soln
5e

HMnO4 + 7H+

Mn2+ + 4 H2O

Balance VO43 V2O3 in basic solution

4e + 2VO43 + 5H2O V2O3 + 10 OH E = 1.37V at pH = 14
4

Quick Review of Redox Rxns

Nernst relation
E = E - (0.059V / n) log Q
What is E (VO43 / V2O3) at pH = 12 ?
E = E - (0.059V / 4) log [OH]10
= E + (10) (0.059V / 4) ( pOH)
= +1.37 V + (0.148) (2)
= +1.66 V
produced)

(E increases with decr pH because OH is

Quick Review of Redox Rxns

Latimer diagrams

1.

Reverse direction, reverse sign

2.

n E are additive, not E

1.5

-1.18

Mn3+ Mn2+ Mn
E = (1) (1.5V) + 2(1.18V) / 3 = 0.28V
3.

E is independent of stoichiometry

Quick Review of Redox Rxns

e- + Fe3+ Fe2+
E = 0.77 V

e- + Fe(OH)3 + 3H+ Fe2+ + 3 H2O

E = E0 - 3(0.059) pH

e- + Fe(OH)3 Fe(OH)2 + OHE = E0 - 0.059 pH

TM redox trends

TM Frost diagrams
at pH=0

Electronegativity increases for

TM going across the rows,
therefore elements become
more difficult to oxidize. A
different way of stating this is
that later TM elements are
stronger oxidants at a given
oxidation state.
This is shown by the increasing
upward slope for oxidation
reactions in Frost diagrams.

TM Pourbaix diagrams

Pourbaix diagrams show increasing E for M/M2+ and M2+/M3+ equilibria

9

Early vs late TMs

2 e + CoO2

Co2+

2 e + TiO2+

Ti 2+

E = 1.66V
E = - 0.14V

Note that CoO2 is unstable in H2O because:

2 e + 4 H+ + CoO2
2 H2O

2 CoO2 + 4 H+

Co2+ + 2 H2O

E = 1.66

O 2 + 4 e + 4 H+

E = -1.23

2 Co2+ + O2 + 2 H2O

E = +0.43

10

TM redox trends
More valence e- going across the rows means higher oxidation states are possible,
but later TM are too electronegative to be oxidized to their group number.

10

11

12

Sc

Ti

Cr

Mn

Fe

Co

Ni

Cu

Zn

+3

+4

+5

+6

+7

+6

+4

+2,3

+2,3

+2

Highest oxidation states accessible

in aqueous solution

11

TM redox trends
Within a triad, 2nd and 3rd row TM are usually
similar.
Example:
Group 6 = Cr, Mo, W triad
Cr3+ is v. stable, unlike Mo3+ and W3+
Cr6+ is a strong oxidizer, unlike Mo6+ and W6+
Generally can get higher ox states for 2nd and
3rd row TMs
Larger ions can have higher CN; CN = 6 is
generally the max in 1st row TM complexes,
but CN = 7-9 common for 2nd and 3rd row TM
[Cr(CN)6]3 (Oh) vs [Mo(CN)8]3 (D4d
square anti-prism)
12

Polyoxometallates
Metal atoms linked via shared ligands, usually corner or edge-shared Td
or Oh
Common for groups 5 (V Nb Ta) and 6 (Cr Mo W)
pH dependence:
high pH

decr pH,

Al(OH)4

VO43

MoO42

no M-O-M

polyoxometallates

decr chg / vol

lower pH

Al2O3 (s)

V2O5(s)

MoO3(s)

extensive M-O-M

13

Vanadates
2 H2VO4- + H+

H3V2O7- + H2O

metavanadate chains, (VO3)

pKa ~ 4

NaVO3

14

Polyoxometallates
decavanadate
has edge-sharing Oh

6 MoO42 + 10 H+ Mo6O192 + 5 H2O

M6O19n ; M = Nb,Ta (group 5); Mo,W (group 6)
There are 6 edge-sharing Oh, each Oh has 1 unique O

4 shared O

4x

1 center O

1 x 1/6

total O / M

3 1/6 = M6O19

15

Keggin structure
[PMo12O40]3

Keggin structures

Td site at cluster center, can also be As,Si,B,Te,Ti

PO43- + 12 WO42- + 27 H+ H3PW12O40 + 12 H2O
http://en.wikipedia.org/wiki/Keggin_structure (ref Fig below)

X2M18O62n
Dawson structure
16

Ferrodoxins

17

Clusters (M-M bonding)

NaReCl4 is
royal blue,
diamagnetic

[Mo2(CH3CO2)4]
Mo-Mo = 2.11

[Re2Cl8]2- D4h
Re-Re = 2.24
< ClReRe = 104

2 Mo(CO)6 + 4 CH3COOH

[Mo2(O2CCH3)4] + 4 H2 + 12 CO

Re(m) has Re-Re = 2.74 and Tm=3180C ; Mo(m) Mo-Mo = 2.80

18

M-M bonding interactions

[M2X8]n common in groups 6-9 (Mo, W, Re, Ru, Rh)

19

Electronic configurations
Cluster

ions

config

b.o.

b.l.

[Mo2(SO4)4]4

Mo(II) d4

242

2.11

[Mo2(SO4)4]3

Mo(II) d4

241

3.5

2.17

Mo(III) d3

20

Electronic configurations
Cluster

ions

config

b.o. b.l.

[Mo2(HPO4)4]2

Mo(III) d3

24

2.22

[Ru2Cl2(O2CCl)4] Ru(II) d6
Ru(III) d5

242**2 2.5

2.27

21

Electronic Configurations

22

Larger Metal Clusters

[Re3Cl12]3-

3 Zr(s) + ZrCl4(g) 4 ZrCl (s)

ZrCl

Zr-Zr bondlengths
intrasheet 3.03
Intersheet 3.42
In Zr (m)

3.19

23

MoCl2 and [Mo6Cl14]2[Mo6Cl14]

2-

HCl (aqu)

MoCl2
4 of the 6 Cl bridge to other Mo6
clusters

For each Mo6:

8 Cl

capping faces

4 ( Cl)

bridging

2 Cl

unique

12 Cl / Mo6 cluster
Similar for M = Mo, W, Nb,Ta
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Groups 8-11
Noble metals : groups 8 11 except Fe, Co, Ni
metallic forms can exist under environment conditions (see Pourbaix diagrams)
Group 11 metals (Cu, Ag, Au) can even exist in strong acid, for example Au does
not react with HCl (conc)
NO3 oxidant, Cl forms stable complex

Au (s)

3 HCl / 1 HNO3

[AuCl4]- (aq) + NO (g)

aqua regia

[Au(CN)2]- (aq)
O2 / CN
25

Group 11
+1 state = d10

no LFSE

- usually CN = 2 linear (VSEPR)

- often disproportionate

AuCl

2 Cu+ Cu (s) + Cu2+ E = +0.36 at pH = 0

1.2
- soft LA

Kf

at pH = 14

I > Br > F
R3P > R3N
S2- > O2

+3 state = d

sometimes Td

- usually D4h square planar (ex AuCl4-)

AuF3

Ni(II)

Cu(III)

Rh(I)

Pd(II)

Ag(III)

Ir(I)

Pt(II)

Au(III)

26

Group 12 (Zn, Cd, Hg)

Not noble metals; Zn, Cd are readily oxidized

pH = 0

Fe/Fe2+

E0 =

+ 0.44V

Cu/Cu2+

E0 =

0.34V

Zn/Zn2+

E0 =

+ 0.76V

Zn(m) is used for

anodic protection
(sacrificial anode)
www.boatzincs.com/shaft.html

Why the aperiodic change from group 11 to 12 ?

BH approach:
Cu

Zn

M (s) M (g)

+ 338

+131 kJ/mol

M (g) M2+ (g) + 2 e

+2704

+2639

M (s) M2+ (g) + 2 e

+3012

+2770
27

Group 12
Group 12 has d10s2 filled orbitals, much weaker MM bonding, and lower IE
MP

Cu 1080C Zn

420 C

Cd

320

Hg

- 39
Zn2+

common CN = 4 (6)

Cd2+

common CN = 6 (4)

Hg2+

common CN = 2 (linear)

Hg2+ is stable in aqu solution

HgCl mercurous chloride (calomel) is [Hg2]2+ 2Cl

bondlengths

Raman band at 171cm1 HgHg stretch

Hg (m)

300 pm

Diamagnetic (Hg+ would be d10s1)

Hg22+

250-270 pm

XRD
28

Hg catenation
Hg32+ linear ion (catenation)
SO2(l)
(6-x) Hg + 3 AsF5 2 Hg3 x/2 AsF6 + AsF3

Superconductor Tc ~ 4 K
Hg3NbF6 2D hex Hg plane

Gray = Hg, white = F, black = Nb

29

f-block elements
Relatively constant electroneg across block (shielding keeps Z* = Z-
nearly constant), so chemistry is very consistent across f-block

Ions have only f valence e

Ce = [Xe]4f2 6s2
Ce3+ = [Xe]4f1

Ce4+ = [Xe]

All Ln have 3+ as their most stable oxidation state

Ce4+ is relatively stable (f)

E0 (Ce4+/ Ce3+) = +1.76V strong oxidant

Eu2+

E0 (Eu2+/ Eu3+) = + 0.35V mild reductant

(f7)

30

Actinide
Frost
Diagrams

31

Pourbaix fblock

32

Ligand interactions
f-block metal ligand interactions:
Ligands have less influence on f orbitals
ff electronic transitions are sharp, relatively independent of
ligand type, and long-lived (slow non-radiative energy
transfer) luminescence
dd transition forbidden
(Laporte selection rules)
Eu(III) 1 % gives bright
orange-red luminescence
Gd2O2S: Pr
Gd(III) = f7 colorless (spin forbidden
transitions)
Pr(III) = f2 green

33

Actinides
actinides +3 oxidation state common, but high ox states also:
Th (f); U U all common
4+

3+

6+

ThO2

ArO22+ linear cation for U, Np, Pu, Am

UO22+ uranyl cation (bright yellow)

High CN common (8-10)

ThCl4

[UO2(NO3)2(OH2)4]
34