Chapter 2 (After Lecture For Students)
Chapter 2 (After Lecture For Students)
Chapter 2 (After Lecture For Students)
Outline
1. The stability of transition metal-carbon bonds
2. Preparation of complexes with metal-carbon bonds
3. Chemical properties of complexes with metal-carbon bonds
4. Related -bonded ligands complexes
[ M-X (X = SiR3, OR, NR2, F, Cl, etc.) ]
5. Metal hydrides
Me
Me
Me
Al
Al
Me
Me
Me
PtCl4 + 4 MeMgI
[Me3PtI]4:
I
Me3Pt
Me3
I
Pt
PtMe3
I
PtMe3
These failures led to the view that transition metalcarbon bonds were unusually weak.
Questions
Are transition metal carbon s bonds really unstable?
What affects M-C bond strength?
What causes the earlier failure to obtain transition metal alkyls
stability
thermal
CH4 + O2 CO2 + H2O
kinetic
G < 0, thermally unstable
Kinetically stable
H = BDE (M-X)
BDE
170
Li-Bu
248
Ti(CH2Ph)4
Ti-CH2R
240
Zn-Me
176
Ti(CH2Si(CH3)4
Ti-CH2R
250
Zn-Et
145
Cp2Ti(CH3)2
Ti-CH3
250
Cd-Me
139
Cp2TiPh2
Ti-Ph
350
Hg-Me
122
(CO)5MnCH3
Mn-CH3
150
Hg-Et
101
(CO)5ReCH3
Re-CH3
220
Zr(CH2C(CH3)4
Zr-CH2R
220
Hg-i-Pr
89
Hg-Ph
136
Zr(CH2Ph)4
Zr-CH2R
380
B-Me
363
Zr(CH2Si(CH3)4
Zr-CH2R
225
B-Et
342
CpPt(CH3)3
Pt-CH3
165
Al-Me
276
(Et3P)2PtPh2
Pt-Ph
250
Al-Et
242
Ta(CH3)5
Ta-CH3
260
Ga-Et
237
W(CH3)6
W-CH3
160
Non-transition metals:
BDE(M-C): 89-280 kJ/mol
[Except B-C]
Transition metals:
BDE (M-alkyl) : 150 - 260
BDE (M-aryl): 250 - 350
Normally, BDE (M-alkyl) <
BDE (M-aryl)
Conclusion: Transition
metal-carbon bond energies
are not so different from
those of main group metals.
LnM
M effect;
Ln effect;
R effect;
a) Metal effect
363
Zn-Me
176
Al-Me 276
Cd-Me
136
Ga-Me 247
Hg-Me
122
150
(PhCH2)3Ti-CH2Ph
240
(CO)5Re-CH3
220
(PhCH2)3Zr-CH2Ph
380
b) R effect (M-R):
[Mn(CO)5C6H5]
170
M-COCH3
[Mn(CO)5CH2C6H5]
87
[Mn(CO)5CH3]
153
[Mn(CO)5COCH3]
129
[Mn(CO)5COC6H5]
89
more electron-withdrawing R.
* M-H is stronger than M-CR3
[Mn(CO)5COCF3]
147
[Mn(CO)5H]
213
[Mn(CO)5I]
195
[Mn(CO)5Br]
252
[Mn(CO)5Cl]
294
Why
alkynyl
(acetylide complexes)
alkenyl
(vinyl complexes)
*
Evidence:
PMe2Ph
Cl
Pt
208 pm
CH2SiMe3
PMe2Ph
Cl
PMe2Ph
PMe2Ph
203
Pt
CH 135 pm
127o
CH2
PMe2Ph
118 pm
198
Pt
C
CH
Cl
PMe2Ph
Why
alkenyl
(vinyl complexes)
alkynyl
(acetylide complexes)
no d-p interaction;
* Evidence:
PMe2Ph
Cl
Pt
208 pm
CH2SiMe3
PMe2Ph
Cl
PMe2Ph
PMe2Ph
203
Pt
CH 135 pm
127o
CH2
PMe2Ph
118 pm
198
Pt
C
CH
Cl
PMe2Ph
Electron-withdrawing group
Encourage backdonation
M
M
Summary:
The M-C bond in transition metal alkyl complexes is not as weak as
was thought previously.
There is no inherent instability of transition metal alkyls.
The BDE(M-R) value increases as the atomic number increases among
the congeners in the same group, in an opposite trend to non-transition
metal alkyls.
The D(M-R) value decrease in the order M(M-H) > D(M-CF3) > D(M-Ph) >
D(M-CH3) > D(M-CH2CH3) > D(M-CH2Ph).
The earlier failure in obtaining TM alkyls is not due to thermodynamic
reasons !
Exercises
Which one has the strongest stability of the following complexes ?
a)
OC
Fe
CH3
OC
Ru
CH3
CO
b)
OC
OC
Fe
OC
CH3
CH3
CO
Fe
OC
CH2CH3
OC
Fe
CH3
CO
Fe
CH2NO2
CO
CO
Fe
CO
OC
CO
CO
c)
Os
OC
Fe
CO
Exercises
Which one has the strongest stability of the following complexes ?
a)
OC
Fe
CH3
OC
Ru
CH3
CO
b)
OC
OC
OC
CH3
CO
CO
Fe
OC
CH3
Fe
OC
CH2CH3
Fe
H
OC
Fe
CO
CH3
Fe
CH2NO2
CO
CO
CO
c)
Os
OC
CO
b) last one
Fe
CO
c) first one]
C
C
transition metal
alkyls?
L nM
R
X
MLn
X = R, H , ....
+ R
common
decomposing
pathways for
transition metal
alkyls?
C
C
*. Reductive elimination
L nM
R
X
MLn
+ R
X = R, H , ....
*. Others,
e.g. -eliminations, intramolecular reactions.
C
C
hydrido-olefin complex
C
H
(A)
(B)
(C)
C. There is a vacant site cis to the alkyl (e.g. (B). but not (C)).
(need an empty orbital to accept C-H electron.)
D. The olefin formed is stable.
E. The metal has e- to go to *(C-H).
Exercises.
(a). It is difficult for the following compounds to undergo hydrogen eliminations. Suggest main reasons.
PEt3
(1)
Cl
Pt
C C H
PEt3
16e
(2)
(3)
OC
OC
R
N
Fe
H2C
N
R2
Co
C
H2
CH3
CH3
R
N
N
OH2 R2
-H2O
R
N
H2C
N
R2
Co
CH3
R
N
N
R2
PEt3
(1)
Cl
Pt
Et3P
16e-
C C H
(2)
OC
OC
Fe
- CO
Fe
CO
CO
C
H2
CH3
CH2CH3
CO
Fe
CH2CH3
18e
16e
CO
CO
Fe
H
CO
CO
Fe
H
CO
Fe
CH2
H
H2C
(3)
R
N
H2C
N
R2
Co
CH3
R
N
N
OH2 R2
-H2O
R
N
H2 C
N
R2
Co
CH3
R
N
N
R2
PEt3
PEt3
(1)
Cl
Pt
CH2
PEt3
(2)
Cl
CH3
PEt3
PEt3
PEt3
(3)Cl
Pt
PEt3
Pt
(4)Cl
Pt
PEt3
(b) Would you expect the following complexes to undergo bH elimination easily?
PEt3
PEt3
(1)
Cl
Pt
CH2
PEt3
(2)
Cl
CH3
Pt
PEt3
after -H elimination
is formed
PEt3
PEt3
(3) Cl
(4)Cl
Pt
Pt
PEt3
PEt3
after -H elimination after -H elimination
is
formed
or
is
formed
(c) Which of the following complexes would you expect to be least stable?
OC
Fe
CO
(a)
If an alkyl
compound can
undergo -H
elimination, it is
unstable.
For above
complexes to
undergo -H
elimination, the
right steps are
needed.
CH2CH3
Ph2P
Fe
PPh2
(b)
CH2CH3
Ph3P
Fe
PPh3
(c)
CH2CH3
(c) Which of the following complexes would you expect to be least stable?
OC
Fe
CO
Ph2P
CH2CH3
(a)
If an alkyl
compound can
undergo -H
elimination, it is
unstable.
For above
complexes to
undergo -H
elimination, the
right steps are
needed.
Fe
PPh2
CH2CH3
Ph3P
(b)
PPh3
CH2CH3
(c)
-L
Fe
L
Fe
CH2CH3
-L
Fe
CH2CH3
18e
16e
L
Fe
H
Fe
H
Fe
CH2
H
H2 C
C
H
(A)
(B)
(C)
For 16 electron complexes, prior ligand dissociation is not required with the
exception of Pd(II) and particularly Pt(II), which do not like to become 18e
complexes.
Thus rate of decomposition of (Ph3P)2PtBu2 to give butane and butene is inversely
dependent upon [PPh3].
The
platinacyclopenta
ne analog
undergoes
decomposition
10,000 times
more slowly.
However larger
platinacycles
undergo
decomposition at
a similar rate to
the dibutyl
complex and by
the same
mechanism.
stable, why?
Me2
P
Ti
H2
C
CH2
Ti
CH2
H
Bonding in M(2-C-H)
M
CR3
CR3
H
(C-H)
M
H
(1)
CR3
(2)
*(C-H)
stable, why?
Me2
P
Ti
H2
C
CH2
Ti
CH2
H
Bonding in M(2-C-H)
M
CR3
CR3
H
(C-H)
M
H
(1)
CR3
(2)
*(C-H)
CH2
M
H
HC
M
-H elim.
CH3
CH2
H
C H
CH2
M
CH2
-CH3 elim.
CH3
CH3
favorable
M
H H
CH2
C
because:
-H elim.
CH2 CH2
-F elim.
F
favorable
M
F
CH2
CH2
CH2
M
H
HC
M
-H elim.
CH3
CH2
H
C H
CH2
M
CH2
-CH3 elim.
CH3
CH3
favorable
M
H H
CH2
C
-H elim.
CH2 CH2
-F elim.
M
F
CH2
CH2
favorable
because: M-H > M-CH3 (by 15-25 kcal/mol); M-F > M-H
b) Reductive elimination
LnM
R
X
+ R
MLn
X = R, H , ....
Pt
Me
Me
PR3
Au
Me
Me
R3P
Pt
R3P Au
PR3
Me
+ H3C CH3
Me + H3C CH3
c) Other pathways
M
-H elimination
For early transition
metal alkyls, hydrogen
elimination can be
an important
decomposition
pathway.
Example
Cp
H
R
H
R
Mo
Cp
Cp
Cp
PR3
CH3
+
Cp
Mo
Cp
H
C PR3
H2
Cp
Mo
H
CH2
C
+
PR3
+
Mo
C
M
Cp
CH3
- PR3
Another example,
H
Cl
Cl
CH2Ph
Ta CH Ph
2
CH2Ph
LiCp*
Ta
- Ph-CH3
Cl
Cl
Ph
CH2Ph
- Ph-CH3
LiCp*
CH2Ph
Ta CH Ph
2
CH2Ph
Cl
H Ph
C
H or
Ta
CH2Ph
Cl
CH2Ph
(a)
C Ph
Ta H
CH2Ph
CH2Ph
(b)
Another example,
H
Cl
Cl
CH2Ph
Ta CH Ph
2
CH2Ph
LiCp*
Ta
- Ph-CH3
Cl
Cl
Ph
CH2Ph
- Ph-CH3
LiCp*
CH2Ph
Ta CH Ph
2
CH2Ph
Cl
H Ph
C
H or
Ta
CH2Ph
Cl
CH2Ph
(a)
C Ph
Ta H
CH2Ph
CH2Ph
(b)
-H elimination. e.g.
CH3
R3P
CH2 CH3
CH
R3P
3
CH2 C
Pt
C
Pt
CH3
R
P
3
CH2 CH
R3P
CH3
CH2
3
C CH3
CH3 C CH3
H3C CH
3
CH3
CH3
CH3 C CH3
CH3
CH3
H
CH2 C CH3
R3P
CH3
Pt
CH2
R3 P
CH2 C CH3
CH3
Exercises.
1) For each pair of complexes listed below, which one is less stable?
H3 C
(1)
(2)
H3C
H 3C
CH3
CH3
CH3
(a)
OC
OC
CH3
PPh3
(a)
(3)
OC
Ph3P
(a)
CH2-CH3
PPh3
OC
OC
CH3
CO
(b)
OC
OC
CH2-CH3
PPh3
(b)
OC
Ph2P
(b)
CH2-CH2-CH3
PPh2
Exercises.
1) For each pair of complexes listed below, which one is less stable?
H3 C
(1)
(2)
H3C
H 3C
CH3
CH3
CH3
(a)
OC
OC
CH3
PPh3
(a)
(3)
OC
Ph3P
(a)
CH2-CH3
PPh3
OC
OC
CH3
CO
(b)
OC
OC
CH2-CH3
PPh3
(b)
OC
Ph2P
(b)
CH2-CH2-CH3
PPh2
Answer:
(1) (a)
reductive
elimination.
(2) (b) -H
elimination.
(3) (a) -H
elimination
is easier
Ru
R 3P
CH3 R P
3
PR3
(a)
Ru
Ru
CH2CH3 R P
2
CH2CH3
PR3
PR2
(b)
(c)
Ru
R3P
CO
(a)
CH3
Ru
R3P
CO
(b)
CH2CH3
H3C
Ru
R3P
(c)
CH3
CH3
PR3
answer: (b)
Ru
R 3P
CH3 R P
3
Ru
PR3
(a)
CH2CH3 R P
2
Ru
CH2CH3
PR3
PR2
(b)
(c)
Ru
R3P
CO
(a)
CH3
Ru
R3P
CO
(b)
CH2CH3
-H elimination
answer: (a).
H3C Ru CH3
CH3
R3P PR3
(c)
Cl
Cl
Cl
Cl
Cl
Me
+ LiMe
Me
Me
Cl
Me
CH2Ph
Ti
Cl
+ PhCH2MgBr
Cl
PhCH2
Ti
CH2Ph
CH2Ph
Ph
Cl
Cl
+ LiCl
Me
Cl
Cl
Me
Zr
Cl
Cl
+?
Ph
Zr
Ph
Ph
Examples:
Cl
Preparation of
homoletic alkyl
complexes:
Cl
Cl
Cl
Me
Me
+ LiMe
Cl
Me
CH2Ph
Ti
Cl
+ PhCH2MgBr
Cl
PhCH2
Ti
CH2Ph
CH2Ph
Ph
Cl
Cl
Me
+ LiCl
Me
Cl
Cl
Me
Zr
Cl
+?
Ph
Zr
Ph
Ph
Cl
PhLi or PhMgBr
Ti
Me
Cl
Cl
+ MeLi
Me
Cl
Me
Me
Cl
Ti
Ti
Cl
Cl
Cl
+ AlMe3
Me
Ti
+ AlMe2Cl
Cl
Cl
CrCl3(THF)3 + MeMgBr
CrMe3(THF)3
CrCl3(THF)3 + AlMe3
CrMeCl2(THF)3
ZnR2isalsoaweakalkylatingreagents.e.g.
Cl
Cl
Nb
Cl
Cl
Cl
+ ZnMe2
Cl
Cl
Nb
Me
Me
Cl
Ph
Ph
Ni
Cl
+ MeLi
Cl
Ph
Pt
Cl
Ph
?
Ph3P
Cl
M Cl
Cl
M = Ti, Zr, Hf
Ph
Ph3P
Ni
Ph
Pt
?
M R
R
R = Ph, CCPh
Me
Me
Ph3P
Ph3P
Ph
Ph
Ni
Cl
+ MeLi
Cl
Ph
Pt
Cl
Ph
Ph3P
Cl
M Cl
Cl
M = Ti, Zr, Hf
Ph
Ph3P
Ni
Ph
Pt
?
M R
R
R = Ph, CCPh
Me
Me
Li(CH2)4Li
PhLi, or PhMgBr
PhCCLi, or
PhCCH/base
CH3
Examples:
+ Me-I
CO
OC
Mn
OC
CO
Mn
OC
CO
+ I-
CO
CO
O
CO
CO
O
CF3
OC
Cl
C
Mn
OC
CF3
CO
CO
CO
+ Cl-
Generation of LnMCO
OC
OC
Mn
CO
OC
CO
Mn CO
OC Mn
Na
CO
O
C
OC
Fe
C
O
Na
Fe
OC
CO
CO
CO
Fe -
OC
CO
CO
Mo
CO
CO
CO
CO
OC
CO
CO
OC
Na+
OC
MoOC
CO
OC
CO
CO
OC
OC
CO
O
C
OC
Ru
C
O
Et
CO
Ru
CO
OC
Ru
OC
Me
OC
CO
CO
OC
CO
-
OC
CO
Et
CO
Na+
EtI
MoOC
OC
OC
W
OC
Et
CO
O
C
OC
Ru
C
O
Ru
OC
CO
Ru
Me
OC
Na
MeI
OC
RuOC
OC
Ru
OC
Me
LnM
LnM
O.S. = 0
O.S. = 2
16e
18e
C.N. = n+2
C.N. = n
CO
Ir
R3P
+ CH3Br
Br
PR3
R3 P
PR3
18e
H 3C
Pt
CO
Ir
Br
16e
R 3P
CH3
+ CH3I
PR3
H 3C
Pt
I
PR3
PR3
Pt
R3P
Ph3P
Ph3P
Pt
PPh3
MeI
Ph3P
Ph3P
Pt
PPh3
MeI
Ph3P
Ph3P
Me
Pt
- PPh3
I
Ph3P
Ph3P
PPh3
I
Pt
Me
or
Ph3P
I
Me
Pt
PPh3
16e
16e
18e
d8, 16e
18e
d8, 16e
H
OC
Mn
OC
CO
CO
CH2
+ CH2N2
Cp2Zr
Mn
OC
CO
Cl
OC
CO
CO
CO
+ CH2=CH-R
Cp2Zr
Cl
CH2 CH R
H
Cp2Mo
H
H
NC
H
H
CN
H
Cp2Mo
CH
CN
CH2 CN
PEt3
Cl
Pt
+ F2C CF2
+ F2C CH2
PEt3
PEt3
Cl
Pt
PEt3
PEt3
Cl
Cl
Pt
PEt3
H
+ F2C CF2
Cl
Pt
PEt3
PEt3
PEt3
PEt3
Pt
+ F2C CH2
Cl
PEt3
Pt
F2
C CF2H
F2
C CH3
PEt3
PEt3
not Cl
Pt
PEt3
H2
C CF2H
Cl
CO
CO
O
C
CH3
Mn
CO
PPh3
CO O
Ir
S
Cl
OC
Mn
OC
CO
CH3 + CO
CO
PPh3
CO
Ir
Cl
Cl
O
PPh3
PPh3
PEt3
Cl
Pt
PEt3
Cl
N N
Et3P
OC
+ SO2
Pt
+ N2
Et3P
Ru
OC
C
O
CH3
OC
Ru
OC
+ CO
CH3
OC
Ph3P
CH3
Equivalent to Ph-
Li2[Cu(CN)Ph]
Fe
OC
Ph3P
H3C
OC
CO
Ph
CH3
Note the geometry
+
Fe
CH3
+ :NuOC
Fe
CO
Nu
LnM
LnM
L
LnM
Ru
OC
Ph3P
+ LiCH2CH2CH2CH3
Cl
OC
How?
Ru
H
PPh3
Ru
OC
Ph3P
+ LiCH2CH2CH2CH3
Ru
OC
CH2CH2CH2CH3
- LiCl Ph3P
18e
Cl
18e
- PPh3
OC
Ru
CH2CH2CH2CH3
16e
Note: 18 16 18 .
OC
Ru
18e
CH2CH3
+ PPh3
OC
Ru
H
PPh3
+ H2C CHCH2CH3
+ RX
X = R, H, ........
e.g.
Me
L
Ph
Rh
I
CO
CO + Me
Rh
L
Ph
Cl
PhCH2
Ta
Cl
CH2Ph
CH2Ph
+ TlCp
Ta
how?
Ph
Cl
PhCH2
CH2Ph
Ta
Ta
+ TlCp
CH2Ph
Cl
Ph
Cl
PhCH2 Ta
Cl
how?
CH2Ph
CH2Ph
PhH2C
+ TlCp
M-Cl + Tl+
TlCl
Ta
CH2Ph
+ TlCl
CH2Ph
Ph
CH
PhH2C
Ta
H2C
Ph
(TS)
Ph
+ CH3Ph
Ta
Ph
CHPh
not PhH2C
Ta
H
CH2Ph
why ?
Cl
PhCH2
Ta
Cl
CH2Ph
Ta
+ TlCp
Ph
Cl
PhCH2 Ta
Cl
how?
CH2Ph
CH2Ph
CH2Ph
PhH2C
+ TlCp
Ta
CH2Ph
+ TlCl
CH2Ph
Ph
CH
PhH2C
Ta
H2C
Ph
CHPh
not PhH2C
Ta
why ?
CH2Ph
(TS)
O. S. of Ta is too high
Ph
+ CH3Ph
Ta
Ph
CH3
OC
OC
Mn
CO
CO
CO
+ CO
OC
OC
C
Mn
CH3
CO
CO
CO
Insertion of alkenes.
Polymerization of olefins, one of the most important catalytic
industrial processes, relies on the facile insertion of alkenes
into metal-alkyl bonds:
LnM R + E
+
LnM
+ E-R
(E+ = H+, Br+ (from Br2), HgCl+ (from HgCl2), even CHCl3 ....)
+
or LnM R
E
+
LnM
-As the metals electronegativity increases, the nucleophilic reactivity of the MC bond decreases.
-Nucleophilic reactivity decreases with more stable carbanions (i.e. -CH 3 <
-C6H5 < -CCR).
Early transition metal alkyls are very sensitive to water and oxygen.
Late transition metal alkyls are more stable to water and oxygen.
Cl-
O
Examples.
Ru
OC
OC
O
+ HCl
+
Ru
Me
Ru
OC
Cl
OC
OC
OC
HBF4
BF4+
Ru
OC
OC
BF4-
O
+
Ru
OC
OC
..
:F:
..
:F
..
B
:F:
..
..
F:
..
Zr
Cl2
Cl
CH2CH3
Zr
HCl
Cl
CH2CH3
Zr
H2O2
Cl
O
Zr
C CH3
Cl
HCl
Zr
Cl2
Cl
Zr
Cl
Cl
CH2CH3
Zr
HCl
Zr
+ ClCH2CH3
Zr
+ CH3CH3
Cl
H2O2
OH
Zr
Cl
Cl
+ HOCH2CH3
O
Zr
C CH3
Cl
HCl
Cl-Cl
Cl
Cl
CH2CH3
Cl
+
Zr
Cl
C CH3
HO-OH,
like Cl-Cl
CH2
CH2
LnM
CH2
CH2
CH2
Precusors to carbene
CH2
CH2
CH2
L nM
CH2
LnM
CH2
CH2
LnM
CH
CH2
CH2
CH2
CH2
CH
CH2
LnM
CH2
CH2
CH2
LnM
CH2
CH2
CH
HC
CH2
A. M-SiR3
*M-Si bond are longer than M-C
* BDE(M-SiR3) may be stronger than BDE(M-CR3)
Reason:
a) some -interaction (Si has empty d orbitals)
b) M-SiR3 is less sterically congested.
*Can LnM-SiCH2R undergo -H elimination?
LnM Si
LnM Si
H
LnM
H
Si
C
LnM
Si
C
Si
filled
unfilled
A. M-SiR3
*M-Si bond are longer than M-C
* BDE(M-SiR3) may be stronger than BDE(M-CR3)
Reason:
a) some -interaction (Si has empty d orbitals)
b) M-SiR3 is less sterically congested.
*Can LnM-SiCH2R undergo -H elimination? Yes.
LnM Si
LnM Si
H
LnM
H
Si
C
LnM
Si
filled
unfilled
Si
C
Yes. But more difficult than M-R since Si=C bond is weaker than C=C
In general, M-SiR3 has properties similar to M-CR3.
M-X
no d-p interaction
possible d-p
interaction
M-X bond is stabilized for 16e or less species (early TM)
unfilled
filled
OR
M
filled
X
filled
OR
Consequences:
M-X can stabilize complexes with less than 18e. e.g.
PR3
H
H
Ir H
PR3
16e, unstable
PR3
H
H
Ir Cl
PR3
16e, stable
t-Bu
OO t-Bu
t-Bu
t-Bu O O
Mo
O
O
O
Mo
O
Why?
14e, stable
Consequences:
M-X can stabilize complexes with less than 18e. e.g.
PR3
H
H
Ir H
PR3
PR3
H
Ir H
PR3
16e, unstable
Mo
PR3
16e, stable
16e, unstable
Ir Cl
PR3
H
H
Ir
PR3
"18e"
..
Cl
t-Bu
OO t-Bu
t-Bu
t-Bu O O
PR3
O
O
Mo
O
Why?
14e, stable
t-Bu
t-Bu O O
Mo
O
.. t-Bu
OO t-Bu
..
Mo
O O
O
"18e"
An angle near 120 suggests that the O is sp2 hybridized and OR- acting as a
4 electron donor .
An angle near 180 suggests that the O is sp hybridized and OR- acting as a
6 electron donor.
6e-
..
O:
..
6e-, if bonding
(2)SimilaritybetweenMCR3andMOR:
BothcanundergoHelimination.
CH2
CH2
CH2
CH2
H
R
CH
M
H
H
C R
+
M
CH2
H2C
O C
+ R
H
M
+ R-CH2-O-
LnM-O-CH2R
Cl
H + O C
H
R
C. M-BR2 complexes
filled
R
B
R
unfilled
Mo
Zr
Cl
PR3
R3P
R3P
Ru
H
R3P
CO
PR3
R3P
H
H
Fe
R3P
OC
OC
Cr
OC
CO
H
H
Q1. Would you expect the H2 molecule in the following complex can
rotate freely? why?
PCy3
CO H
W
H
PCy3
OC
OC
H
H
H
H
Q1. Would you expect the H2 molecule in the following complex can
rotate freely? why?
PCy3
CO H
W
H
PCy3
OC
OC
H
H
H
H
+
Ph2P
Ph2P
(b)
P
Ph2
In terms of bonding:
Fe
vs
PPh2 H
+
Ph2P
CO
Mo
H
PPh2 H
CO
Et2P
PPh2
Mo
vs
PPh2
P
Et2
PEt2
PEt2
H
H
Os
M
H
H
H
+
Ph2P
Ph2P
(b)
P
Ph2
In terms of bonding:
Fe
vs
PPh2 H
+
Ph2P
CO
Mo
H
PPh2 H
CO
Et2P
PPh2
Mo
vs
PPh2
P
Et2
PEt2
PEt2
H
H
Os
M
H
H
H
H-H bond will break when there is excessive backdonation from M to *(H2). For
(a), Os has stronger backdonating ability than (b).
For (b), Et is more electron-releasing than Ph, leading to stronger backdonation.
e.g.
H
Si
H
N
or
H
X
In terms of bonding:
similar to M( 2-H2)
For example,
Cl
Ph3P
H
Ru
Cl
PPh2
Cl
Ph3P
agostic
Mn
OC
OC R3Si
Me2P
Me2P
Ti
CH2
Cl H
Cl
agostic
CH2
Additional examples
N
Rh
Pt
L
OC
OC
Mn
SiHPh2
H
2-H
H
M
M
(bent)
3-H
H
M
Examples:
Cp2Nb
R3P
R3P
Re
NbCp2
H
H
H
H
Cp2
Lu
H
PR3
Re
H
PR3
Cp2Lu
LuCp2
H
M ?
For electron counting purpose, we can use the resonance structures like:
H
H
M
OC CO
OC
CO
Re
Re
H
H
CO
CO
CO CO
OC
OC
Re
OC
OC
Re
H
CO
CO
CO CO
For electron counting purpose, we can use the resonance structures like:
H
H
M
OC CO
OC
CO
Re
Re
H
H
CO
CO
CO CO
OC
OC
Re
OC
OC
Re
H
CO
CO
CO CO
(5) BH4-, BH3L, and AlH4- complexes. A variety structures are possible.
e.g. for BH4-
H
M
H
M H B
H
H
B
H
2BH4
1-BH4
H
B
3-BH4
H
H
M
H
M
B
H
4
M
H
H
B
M
2
H
M
B
H
M
H H
M
H
+
M
- H
B
H
H
M(BH4) M+ + BH4H
+
M
B
H
M(BH4) MH + BH3
Covalent model:
+
M
- H
B
H
B
H
M
H
H
M(BH4) M+ + BH4-
- H
B
H
H
+
M
2e
4e
- H
B
+
M
H
H
H
B
H
1e
6e
Covalent model:
M(BH4) MH + BH3
H
H
H
M
M
B H
B
H
H
H
H
3e
5e
CO
Fe
HBF4
CO
CO
OC
H
OC Fe
CO
BF4-
CO
OC
CO
OC
H
W H
H
HBF4
W
H
Ph3P
PPh3
Ni
HCl
PPh3
CO
OC
+
H
Ph3P
Ph3P
BF4-
+
Ni
H
PPh3
+
Ph2P
Ph2P
Ru
HBF4
H
Fe
Ph2P
Ph2P
Ru
H
H
BF4-
Cl-
LiAlH4
PPh3
H
H
Ir
Ph3P
H
Ph3P
Ir
Cl NaBH4 H
PR3
Ir
H
R3P
H
H
R3P
PR3
BH2 :L
Ir
H
L
R3P
+ H3B:L
(3) From H2
LnM + H2
16e
Ln M
Ph3P
Ph3P
OC
Ph3P
Rh
16e
Ir
16e
PPh3
Cl
PPh3
Cl
R + H2
Ln M
Ph3P
Ru
16e
PPh3
Cl
or
LnM
18e
L nM
H
H
+ R-H
16e
H
+ H H
Ph3P
Ph3P
PPh3
Rh
18e
Cl
H
+ H H
OC
Ph3P
PPh3
Cl
PPh3
Ir
18e
H
Cl
PPh3
+ H H
Cl
Ru
Ph3P
18e H H
PPh3
Cl
:NEt3 Cl
Ph3P
- HNEt3Cl
PPh3
Ru
16e
PPh3
H
Me
Me
Me
Me
Me
+ 6 H2 + 3 PMe2Ph
Me
WH6(PMe2Ph)3 + 6 CH4
18e
Me
Zr
Me
H
Zr
+ 2 H2
+ 2 CH4
M CH3 + H H
M H + H CH3
H
M
M H + H R
R
H
(b) M R + H H
H
M R
M H + H R
Me
Me
Me
Me
+ 6 H2 + 3 PMe2Ph
Me
Me
WH6(PMe2Ph)3 + 6 CH4
18e
Me
Zr
Me
H
Zr
+ 2 H2
+ 2 CH4
M CH3 + H H
M H + H CH3
H
M
M H + H R
R
H
(b) M R + H H
H
M R
Answer: (b)
W(VI) and Zr(IV)
Can not be
oxidized
M H + H R
Cl
Ph3P
PPh3
PPh3
Ru
Cl
+ NaOCHMe2 + PPh3
Ph3P
Ph3P
M-H
PPh3
PPh3
Ru
H
H
+ NaCl +
how?
Q1
Cl
Ph3P
PPh3
PPh3
Ru
+ NaOCHMe2 + PPh3
Cl
PPh3
PPh3
Ru
OCHMe2
Cl
Ph3P
Ph3P
Me2CHO
Ph3P
Ph3P
Cl
Ph3P
Ph3P
+ PPh3
Ph3P
PPh3
PPh3
Ru
Cl
NaOCHMe2
Cl
PPh3
PPh3
Ru
H
PPh3
PPh3
Ru
H
H
PPh3
PPh3
Ru
H
PPh3
PPh3
Ru
H
C
Ph3P
PPh3
PPh3
Ru
H
H
Q2
Any RO- with -H
should work.
Therefore NaOMe,
NaOEt will give the
same product.
-H is incorporated
to M.
Q3
NaOCD(CH3)2 =>
RuD2(PPh3)4
NaOCH(CD3)2 =>
RuH2(PPh3)4
PEt3
Cl
Pt
PEt3
CH2CH3
Cl
PEt3
Fe
OC
Ph3P
Pt
how?
PEt3
Cl
+ LiCH2CH2CH2CH3
Fe
OC
Ph3P
+
H
LiBu
LiCl
Fe
OC
Ph3P
detailed mechamism?
PEt3
Cl
PEt3
Pt CH2CH3
Cl
Pt H
PEt3
Cl
PEt3
PEt3
PEt3
Pt CH2
Pt CH2
PEt3
how?
Cl
CH2
Fe
OC
Ph3P
Cl
PEt3
CH2
+ LiCH2CH2CH2CH3
Pt
Cl
PEt3
CH2
H
Fe
OC
Ph3P
PEt3
CH2
+
H
LiBu
LiCl
Fe
OC
Ph3P
detailed mechamism?
Ph3P
Ph3P
H
Ir
PPh2
Cl
H
Ph3P
Ir
PPh3
PPh2
Cl
Na+ + H-
H+ + Cl-
Ph3P
Ph3P
H
PPh3
PPh3
Ru
H
H
hydridic M-H !
M+ + H +
Ph3P
PPh3 BF4
PPh3
Ru
H
M- + H +
H
OC Co
CO
CO
CO
Acidic M-H !
CO CO
pKa = 8.3
+ H+
OC Co
CO
(ii)FactorsinfluencinghydridicandacidicpropertiesofMH:
LnM
M-H-
M-H+
PropertiesofMHaredependentontheedensityonM.
Ingeneral,increaseinelectronrichnessofmetalcenter,will
>decreaseacidiccharacters
>increasehydridiccharacters
Exercises.
For each of the following pairs, which one is more acidic, which one is
more hydridic?
(a) H-Co(CO)4 vs H-Co(CO)3(PPh3)
(c)
CpRu(CO)2H vs CpOs(CO)2H
For each of the following pairs, which one is more acidic, which one is
more hydridic?
(a) H-Co(CO)4 vs H-Co(CO)3(PPh3)
H-Co(CO)4 is more acidic.
H-Co(CO)3(PPh3) is more hydridic.
Because PPh3 is more e- donating.
CpRu(CO)2H vs CpOs(CO)2H
CpRu(CO)2H is more acidic.
CpOs(CO)2H is more hydridic.
Because Os complexes are more e- rich.
General trends:
- pKa generally decreases as you move down a column
- pKa generally increases as you move to the right across the
transition series
- electron donating substituents decrease pKa values
H + B:
M
e.g.
M- + BH+
+ E+
M+ + E-H
e.g.
WH6(PMe3)3 + HBF4 + 3 MeCN ----->
[WH2(MeCN)3(PR3)3]2+ + H2
C. Insertion reactions
H +A
M
e.g.
H
OC
Mn
OC
CO
CO
+ CH2N2
CO
Cp2Zr
Cp2Zr
Cl
H
H
H
+ CH2=CH-R
+ 2 CH2=O
C. Insertion reactions
H +A
e.g.
H
OC
Mn
OC
CO
CO
CH2
+ CH2N2
CO
Cp2Zr
Cp2Zr
OC
Mn
OC
CO
CO
CO
Cl
H
H
H
+ CH2=CH-R
+ 2 CH2=O
Cp2Zr
Cp2Zr
Cl
CH2 CH R
H
CH2
H
O
O
CH2
H