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Electron Counting: Understanding Structure and Reactivity
Electron Counting: Understanding Structure and Reactivity
2 Electron Counting
Predicting reactivity
dissociative
(C2H4)PdCl2
- C2H4 CO
(C2H4)2PdCl2 (C2H4)(CO)PdCl2
?
CO - C2H4
(C2H4)2(CO)PdCl2
associative
3 Electron Counting
Predicting reactivity
18-e PdII
4 Electron Counting
Predicting reactivity
dissociative
Cr(CO)5
- CO MeCN
Cr(CO)6 Cr(CO)5(MeCN)
?
MeCN - CO
Cr(CO)6(MeCN)
associative
5 Electron Counting
Predicting reactivity
16-e Cr(0)
18-e Cr(0)
18-e Cr(0)
6 Electron Counting
The basis of electron counting
s px py pz
7 Electron Counting
The basis of electron counting
8 Electron Counting
Compounds are not always
electron-precise !
9 Electron Counting
Compounds are not always
electron-precise !
10 Electron Counting
Prediction of stable complexes
11 Electron Counting
If there are not enough electrons...
12 Electron Counting
Reactivity of electron-deficient compounds
hν
Fe(CO)5 Fe(CO)4 THF Fe(CO)4(THF)
- CO
13 Electron Counting
If there are too many electrons...
• "Too many electrons" means there are fewer net covalent bonds
than one would think.
– Since not enough valence orbitals available for these electrons.
• An ionic model is required to explain part of the bonding.
• The "extra" bonds are relatively weak.
• Excess-electron compounds are relatively rare,
especially for transition metals.
• Often generated by reduction (= addition of electrons).
14 Electron Counting
Where are the electrons ?
15 Electron Counting
Metal-centered lone pairs
H+
Cp2WH2 Cp2WH3+
Basicity of Cp2WH2 comparable to that of ammonia!
16 Electron Counting
How do you count ?
"Covalent" count:
1. Number of valence electrons of central atom.
• from periodic table
2. Correct for charge, if any.
• but only if the charge belongs to that atom!
3. Count 1 e for every covalent bond to another atom.
4. Count 2 e for every dative bond from another atom.
• no electrons for dative bonds to another atom!
5. Delocalized carbon fragments: usually 1 e per C
6. Three- and four-center bonds need special treatment.
7. Add everything.
There are alternative counting methods (e.g. "ionic count").
Apart from three- and four-center bonding cases,
they should always arrive at the same count.
We will use the "covalent" count in this course.
17 Electron Counting
Starting simple...
H N= 5
N
H H H= 1 H 3* H⎯ = 3
H⎯ = 1 H + ⎯⎯
H H
+ ⎯⎯ e-count 8
H
e-count 2
N N has a lone pair.
H Nucleophilic!
H
H C= 4
H 4* H⎯ = 4 H H
C C= 4
H + ⎯⎯
2* H⎯ = 2
H e-count 8 C C
2* C⎯ = 2
H H H + ⎯⎯
H e-count 8
H H
C
C C
A double bond counts
H as two covalent bonds.
H H H
18 Electron Counting
Predicting reactivity
H H
C= 4 C= 4
H C + chg = -1 C 2* H⎯ = 2
3* H⎯ = 3 + ⎯⎯
H + ⎯⎯ H e-count 6
H e-count 6
C H H "Singlet carbene". Unstable.
Highly reactive,
H C Sensitive to nucleophiles
electrophilic.
H
(empty orbital)
and electrophiles (lone pair).
H
C= 4
H C - chg = +1
H "Triplet carbene". Extremely
3* H⎯ = 3
reactive as radical, not
H + ⎯⎯ C
especially for nucleophiles
H
e-count 8 H
or electrophiles.
C
Saturated, but
H
H nucleophilic.
19 Electron Counting
When is a line not a line ?
H H
H H
H B N
H C C
H H H
H H H
is
C= 4 H H H H
3* H⎯ = 3
C⎯ = 1 H B N or H B N
+ ⎯⎯ H H H H H H
e-count 8
B= 3 N= 5
B= 3
N= 5 - chg = +1 + chg = -1
3* H⎯ = 3
3* H⎯ = 3 3* H⎯ = 3 3* H⎯ = 3
N→ = 2
+ ⎯⎯ N⎯ = 1 B⎯ = 1
+ ⎯⎯
e-count 8 + ⎯⎯ + ⎯⎯
e-count 8
e-count 8 e-count 8
20 Electron Counting
Covalent or dative ?
How do you know a fragment forms a covalent or a dative bond?
Cl PPh3 Cl PPh3
Pd 1e Pd = 10
covalent dative Pd 2e
Cl⎯ = 1
bond bond
P→ = 2
allyl = 3
+ ⎯⎯
"bond" to the 3e e-count 16
allyl fragment
21 Electron Counting
Handling 3c-2e and 4c-2e bonds
B B
H H
H
22 Electron Counting
Handling 3c-2e and 4c-2e bonds
Rewrite bonding in terms of two BH3 monomers:
2e B= 3
H H H 1e 3* H⎯ = 3
B B BH→ = 2
HH + ⎯⎯
H e-count 8
This is one of the few cases where Crabtree does things differently
(for transition metals).
The method shown here is closer to the actual VB description of
the bonding.
23 Electron Counting
What kind of bridge bond do I have ?
A 3c-2e bond will only form when the central (bridging) atom
does not have any lone pairs.
When lone pairs are available, they are preferred as donors.
Me Cl
Me Me Cl Cl
Al Al Al Al
Me Me Cl Cl
Me Cl
A methyl group can form
one more single bond. After After chlorine forms a single bond,
that, it has no lone pairs, so the it still has three lone pairs left.
best it can do is share the Al-C One is used to donate
bonding electrons with a to the second Al:
second Al: Al = 3 Al = 3
Me Me Cl Cl Cl
Me 3* Me⎯ = 3 3* Cl⎯ = 3
Al Al MeAl→ = 2 Al Al Cl→ = 2
Me Me Me + ⎯⎯ Cl Cl + ⎯⎯
e-count 8 Cl e-count 8
24 Electron Counting
3c-2e vs normal bridge bonds
25 Electron Counting
Handling charges
"Correct for charge, if any, but only if it belongs to that atom!"
How do you know where the charge belongs?
26 Electron Counting
Handling charges
Even overall neutral molecules could have "hidden" charges!
A boron atom with 4 bonds
B would be -1 (c.f. BH4-). B
Co = 9
No other obvious centers of + chg = -1
Ph2P PPh2 charge, so the Co must be +1. Ph2P PPh2 3* P→ = 6
Ph2P Ph2P 2* CO→ = 4
Co Co + ⎯⎯
e-count 18
OC CO OC CO
27 Electron Counting
A few excess-electron examples
PCl5 P would have 10 e, but only has 4 valence orbitals, SiF62-, SF6, IO65- and
so it cannot form more than 4 “net” P-Cl bonds. noble-gas halides can
You can describe the bonding using ionic structures be described in a
("negative hyperconjugation"). similar manner.
Easy dissociation in PCl3 en Cl2.
"PBr5" actually is PBr4+Br- !
Cl Cl Cl
Cl
Cl Cl
Cl P Cl P Cl
P Cl Cl P Cl
Cl Cl
Cl Cl
Cl Cl
Cl ? Cl
P= 5
P= 5 + chg = -1
5* Cl⎯ = 5 4* Cl⎯ = 4
+ ⎯⎯ + ⎯⎯
e-count 10 e-count 8
28 Electron Counting
A few excess-electron examples
HF2- H only has a single valence orbital, This is just an extreme form of
so it cannot form two covalent H-F bonds! hydrogen bonding. Most other
-
Write as FH·F , mainly ion-dipole interaction. H-bonded molecules have
less symmetric hydrogen bridges.
O H O
F H F
F H F ?
O H O
F H F F H F
H= 1 H= 1 O O
- chg = +1 1* F⎯ = 1 H
2* F⎯ = 2 + ⎯⎯
+ ⎯⎯ e-count 2
e-count 4
29 Electron Counting
Does it look reasonable ?
30 Electron Counting
Electron-counting exercises
31 Electron Counting
Oxidation states
32 Electron Counting
Calculating oxidation states
33 Electron Counting
How do you calculate oxidation states ?
34 Electron Counting
Examples - main group elements
CCl4 AlCl4-
Cl Cl Cl Cl
Cl Cl Cl Cl
C C Al Al
Cl Cl Cl Cl
Cl Cl Cl Cl
no chg = 0 - chg = -1
4* Cl-⎯C+ = +4 4* Cl-⎯Al+ = +4
+ ⎯⎯ + ⎯⎯
ox st +4 ox st +3
COCl2
Cl Cl no chg = 0
2* Cl-⎯C+ = +2
O C O C O2-=C2+ = +2
Cl Cl + ⎯⎯
ox st +4
35 Electron Counting
Examples - transition metals
PdCl42- Cl Cl Cl Cl 2- chg = -2
Pd Pd 4* Cl-⎯Pd+ = +4
+ ⎯⎯
Cl Cl Cl Cl ox st +2
O no chg = 0
MnO4- O
1* O-⎯Mn+ = +1
Mn 3* O2-=Mn2+ = +6
Mn O
O O
O + ⎯⎯
O
O ox st +7
O O
- chg = -1
2- 2+
4* O =Mn = +8
Mn Mn
O O + ⎯⎯
O O ox st +7
O O
36 Electron Counting
Examples - homonuclear bonds
C2Cl6 Cl Cl Cl Cl no chg = 0
Cl Cl 3* Cl ⎯C = +3
- +
C C C C 1* C⎯C = 0
Cl Cl
+ ⎯⎯
Cl Cl Cl Cl
ox st +3
Pt2Cl64- Cl Cl 2- chg = -2
Cl Cl 3* Cl-⎯Pt+ = +3
Cl Pt Pt Cl Cl Pt Pt Cl 1* Pt⎯Pt = 0
Cl Cl + ⎯⎯
Cl Cl ox st +1
Artificial, abnormal formal oxidation states. If you want to say something about stability,
pretend the homonuclear bond is polar
(for metals, typically with the + end at the metal you are interested in).
For the above examples, that would give C(+4) and Pt(+2), very normal oxidation states.
37 Electron Counting
Example - handling 3c-2e bonds
H H H H H H H
H H
B B B B B B
H H HH HH
H H H
no chg = 0
3* H-⎯B+ = +3
+ ⎯⎯
ox st +3
38 Electron Counting
Oxidation state and stability
MgMe4
Me Me Me Me no chg = 0
Mg Mg 4* Me ⎯Mg = +4
- +
+ ⎯⎯
Me Me Me Me ox st +4
39 Electron Counting
Significance of oxidation states
40 Electron Counting
Normal oxidation states
41 Electron Counting
Oxidation-state exercises
Calculate oxidation states for the metal in the complexes below.
From this and the electron count (done earlier),
draw conclusions about expected stability or reactivity.
Me2Mg Pd(PMe3)4 MeReO3
ZnCl4 Pd(PMe3)3 OsO3(NPh)
ZrCl4 ZnMe42- OsO4(pyridine)
Co(CO)4- Mn(CO)5- Cr(CO)6
V(CO)6- V(CO)6 Zr(CO)64+
PdCl(PMe3)3 RhCl2(PMe3)2 Ni(PMe3)2Cl2 -
Ni(PMe3)Cl4 Ni(PMe3)Cl3 PMe3
Cl Pd
Me3P
BMe3
42 Electron Counting
Coordination number and geometry
43 Electron Counting
π-system ligands
H CO
CO
Co Co
OC CO OC CO
CN 3 or 5
44 Electron Counting
Common coordination numbers
45 Electron Counting
Coordination number and geometry
46 Electron Counting
Example: protonation of WH6(PMe3)3
H H
Could WH6(PMe3)3 Me3P H
be a true polyhydride ?
Me3P W PMe3
H H
H Count: 18-e (OK).
Oxidation state: 6 (OK).
CN: 9 (very high).
Possible.
47 Electron Counting
Example: protonation of WH6(PMe3)3
+
Protonation gives WH7(PMe3)3+. Me P H HH
3
Could that still be
a true polyhydride ? Me3P W HPMe3
H H
H Count: 18-e (OK).
Oxidation state: 8 (too high).
CN: 10 (extremely high).
Virtually impossible.
W+ has only 5 electrons
but must form 7 W-H bonds !
This is almost certainly
a dihydrogen complex.
48 Electron Counting