-- 1 --

CHEM4680 - Organometallic Chemistry

Final exam, April 22, 2008 - Rough answers
1. Counting
Cl
Nb
Cl
Cl
Cl
Cl
Cl
Cl
Nb
Cl
Cl
Cl

Nb 5
5*Cl- 5
1*Cl 2
tot: 12
Nb
V

Count is low. But oxidation state is OK,
and more than 6 Cl atoms likely would not
fit. There might be some extra
stabilization through -donation of Cl lone
pairs to Nb.
(OC)
5
Mn Ge
Cl
O

Mn 7
5*CO 10
Ge- 1
tot: 18
Mn
I

Ge 4
Cl- 1
Mn- 1
O 2
tot: 8
Ge
(0)
(counting Mn
+
-Ge
-
)
The counts for both Mn and Ge are OK.
Mn is in a rather low oxidation state, but
the 5 CO ligands are good -acceptors and
should stabilize this well. Ge is also in a
low oxidation state (Ge
IV
would be more
normal). This is partly artificial, as we
count Mn
+
-Ge
-
, but still Ge only has two
covalent bonds, i.e. comparable to a
carbene. The lower oxidation states are
more normal for the heavier main-group
metals (Sn, Pb). Ge is coordinatively
saturated, but one could still expect some
reactivity at the Ge center (possibly after
dissociation of THF)
P
Pd
tBu
tBu
P
Pd
tBu
tBu
Br Br

Pd 10
Br- 1
Pd- 1
C=C 2
P 2
tot: 16
Pd
I

Square-planar 16-e Pd
II
is normal and
stable. Here, the formal oxidation state of
+I is artificial because of the Pd-Pd bond.
No reason to expect a stability very
different from e.g. a
Br
2
Pd(phosphine)(olefin) complex.
Cl
Pt
Cl
Cl
Me
2
P
SO
3
2-

The sulfonic acid group carries a 1-
charge, so the charge on the Pt fragment is
only -1!
Pt 10
3*Br- 3
-1 1
P 2
tot: 16
Pt
II

Square-planar 16-e Pt
II
is normal and
stable.
-- 2 --
2. Main-group metals
a) EtLi could act as a base, deprotonating the Me group at carbon. This would give a
delocalized anion, which would probably not react further with EtLi. On work-up, it would
re-generate the starting material or hydrolyze to give acetophenone.
N
CH
3
Ph
CH
3
EtLi
- EtH
N
CH
2
Ph
CH
3
Li
N
CH
2
Ph
CH
3
Li
H
+
H
2
O
N
CH
3
Ph
CH
3
H
+
H
2
O
O
CH
3
Ph

Some reduction through -hydrogen transfer is possible, giving an unwanted secondary
amine on work-up. This type of reaction is typically more important for Al.
N
CH
3
Ph
CH
3
N
CH
3
Ph
CH
3
Li
H
H
+
H
2
O
HN
CH
3
Ph
CH
3
H
EtLi
- C
2
H
4
C
N
Li
H

Single-electron transfer (and further reactions from there) would also be possible, although
those would be more likely for diarylimines.
Metallation at the phenyl ring, ortho to the imine group is also possible. As with
deprotonation of the methyl group, workup would re-generate the starting material or give
acetophenone.
b1) C-F bonds are very unreactive, the Grignard would not form. But if you would make the
Grignard via a different route, it would most likely react with the imine.
b2) Metal-halogen exchange only works with polar organometallics, typically organolithium
reagents. The Si-C bond is nearly apolar and far to unreactive for this. For the same reason,
the new Si-C bond formed would not react with the imine.
b3) This ortho-metallation is likely to work as written, and the resulting aryllithium
compound should react with the imine. Deprotonation (similar to EtLi above) might be a
complicating factor.
3. Transition metals (1)
a) The starting complex is 18-e and cannot bind PMe
3
in this form. It could dissociate CO
first, but that makes it hard to explain the final product. Insertion of CO in the metal-Cp*
bond is unlikely until the ring has become
1
-bound. Ring slippage is the most likely initial
step. After binding of the first PMe
3
, another slippage step is needed at some point.
Pt
CO I
PMe
3
Pt
CO I
Pt I CO
PMe
3
Pt I CO
PMe
3
Pt
I
CO
PMe
3
Me
3
P
Pt
I
PMe
3
Me
3
P
O
PMe
3
18e 16e 18e
16e 18e 16e

-- 3 --
b) A third-row transition metal like Pt forms stronger metal-ligand bonds than second-row
metal Pd. No oxidation or reduction is involved. Ring slippage costs energy, and for CO
insertion a metal-carbon bond has to be (partially) broken; either of these steps might be rate-
limiting, and they should both be faster for Pd. Capture of PMe
3
is unlikely to be rate-
determining; this step should be slower for Pd.
c) Complex 6 is 16e and so could be reactive. Oxidative addition of H
2
and reductive
elimination of H with the acyl group would give (PMe
3
)
2
Pt(H)(I) and Cp*CHO. This latter
compound could conceivably (but not very likely) insert in the Pt-H bond, after which further
reaction with H
2
might produce Cp*CH
2
OH. Also, hydrogenation of the two C=C bonds of
Cp*CHO could be catalyzed by the Pt fragment. Finally, (PMe
3
)
2
Pt(H)(I) might decompose to
Pt metal, PMe
3
and HI or Me
3
PH
+
I
-
.
4. Transition metals (2)
a) Starting complex 7 is 18-e if we count its -agostic interaction. So the agostic interaction
first has to be lost, then the Si-H bond can enter, add, and the hydride can eliminate together
with the alkyl group. Instead of the combination of oxidative addition/reductive elimination,
one can also write a single -bond metathesis step, which is perhaps more likely (since the
oxidative addition forms Co
V
!).
Co
CH
2
L
CH
2
H
+
Co
SiEt
3
L
+
Et
3
SiH
18e
Co
CH
2
L
CH
3
+
Co
CH
2
L
CH
3
+
Et
3
Si H
Co
CH
2
L
CH
3
H
Et
3
Si
+
- C
2
H
6
dissoc
assoc
ox add
red elim
18e
18e 16e
16e

b) Reversible -elimination and rotation of the terminal Me group eventually exchange both
carbons and all five hydrogens of the ethyl fragment:
Co
CH
2 L
CH
2
H
+
Co
L
H
+
CH
2
CH
2
Co
L
H
+
CH
2
CH
2
Co
CH
2 L
CHH
H
+
Co
CH
2 L
CH
2
H
+
elimination/insertion Me rotation

Rotation of the CH
3
group is normally very easy, and will probably not be frozen out by
cooling. Freezing out the elimination will produce a "normal" Et pattern, i.e. a quartet (2H)
for the CH
2
group and a triplet (3H) for the CH
3
group. Should it be possible to freeze out
even the CH
3
rotation, then one might expect a 2:2:1 pattern. However, the complex would
most likely be chiral (three-legged piano-stool), in which case all 5 protons of the C
2
H
5
group
would become inequivalent.
-- 4 --
c) The agostic interaction with the CH
2
Si carbon needs to be broken, then there is free
rotation around the Co-C bond, -elimination to the terminal carbon can take place, rotation
around to Co-olefin bond, and finally re-insertion gives the terminal alkyl species.
Co
CH
2
L
CH
H
CH
2
SiEt
3
+
Co
CH L
CH
2
H
CH
2
SiEt
3
+
Co
L
H
+
CH
2
CH
CH
2
SiEt
3
Co
CH L
CH
H
SiEt
3
CH
3
+
Co
L
H
+
CH
CH
2
CH
2
SiEt
3
dissoc,
rot,
assoc
elim
rot
ins

d) Breaking the agostic interaction is likely to be facile. Secondary alkyls are more electron-
rich than primary alkyls (alkyl groups are electron-donating!), so electronically the Si-H
oxidative addition (and the -bond metathesis) step should be easier for the secondary alkyl.
However, the secondary alkyl is much more hindered than the primary alkyl, and apparently
that is enough to prevent easy reaction with the bulky Et
3
SiH reagent.
5. See attached paper by Goldberg
(J. Am. Chem. Soc. 2007, 129, 3460)
a) Writing out the structure helps
N
N
Pt
Me
Me
iPr
iPr
iPr
iPr
Me

There is one covalent and one dative Pt-N bond, and three covalent Pt-C bonds, so:
Pt 10
3*Me- 3
N- 1
N 2
tot: 16
Pt
IV

Pt
IV
normally has a preference for 18-e. The relative stability of the complex, despite the low
electron count, could be due to (1) the steric hindrance provided by the iPr groups on the
ligand, and (2) -donation from the anionic N
2
ligand.
-- 5 --
b) The complex itself contains no D, and no D
2
or similar is added, so they must come from
the solvent, which is benzene-d
6
.
c) The C-H activation and -elimination/re-insertion that the whole paper is about involves
the iPr groups of the ligand. This is also clear from the X-ray structure in Figure 1, where the
C=C bond of a dehydrogenated iPr group is coordinated to the metal. There were originally
28 hydrogens in the four iPr groups, but 1 H is lost in a reductive elimination (third step, -CH
4

in Scheme 2), leaving 27 H's in these side groups, which all become deuterated. See also (10)
under References.
N
H
N
CD
2
CD
3
C
3
D
7
D
7
C
3
D
7
C
3
Pt
D
2b-d
27