CHEM4680: Organometallic Chemistry

Mid-term examination, February 26, 2009

1
a) Mo 6
Cp*- 5
Me- 1
2*O= 4
-------------
total 16
Ox state: Cp*
-
, Me
-
, 2*O
2-
:
Mo
VI
The oxygen atoms also have
lone pairs which could do
additional -donation to Mo.
Could be an OK compound,
might associate via bridging
oxygens (but the large Cp*
might hinder that).
b) Cr 6
6*NH
3
12
-------------
total 18
Ox state: Cr
(0)
Count OK, but ox state low for
Cr, and there are no -acceptor
ligands, only -donors: this
should not be stable.
c) Various ways of counting
depending on where you put
the positive charge and how
you draw the bonds (dative vs
covalent) to the bridging
oxygen. But you should
always arrive at two 16-e Pd
II

centers. Normal oxidation
state and count, should be
stable. The drawing suggests
there might be a steric
problem for the two MeCN
molecules, but that is hard to
judge from such a simple
drawing.
d) The tricky part is realizing
the B atom must have a
negative charge (as in BH
4
-
).
This means the Rh must have
a corresponding positive
charge.
Rh 9
2*Py 4
2*C=C 4
+ chg -1
-------------
total 16
Ox state: + chg: Rh
I
Normal oxidation state and
count, should be stable.
e) For every N atom, one bond
to Al must be covalent, the
other dative.
Al 3
N- 1
N 2
2*Me- 2
-------------
total 8
Ox state: N
-
, 2*Me
-
: Al
III
Normal count, oxidation state
and coordination number.
Should be OK. You might
expect reactivity because of
the presence of both acidic NH
bonds and reactive Al-C bonds
within the same molecule.
f) Now all Al-N bonds must
be covalent.
Al 3
2*N- 2
tBu- 1
-------------
total 6
Ox state: 2*N
-
, tBu
-
: Al
III
Ox state OK, but count low.
Would want to form higher
aggregates, but the bulky tBu
groups might hinder that.
There could be some
stabilization through NAl -
donation, since every N has a
lone pair.

2
a) The N-Sn bond must be dative, the other bonds to Sn are covalent:
Sn 4
N 2
2*Me- 2
Ar- 1
AcO- 1
-------------
total 10
Four covalent bonds: Sn
IV
.
Sn is large, so counts larger than 8 can occur.
b) Somehow the coordinated and dangling Me
2
N group must exchange. If they do, at high
temperature you will see for both Me(N) and CH
2
(N) the average of the coordinated and non-
coordinated situation. Two reasonable mechanisms are:
Sn
NMe
2
Me
Me
Me
2
N
OOCMe
Sn
NMe
2
Me
Me
Me
2
N
OOCMe
Sn
Me
Me
Me
2
N
OOCMe
Me
2
N
Sn
NMe
2
Me
Me
NMe
2
+
CH
3
COO
-

c) The Me(Sn) groups see exactly the same environment before and after the exchange of the
Me
2
N groups. So, you will see a singlet (with Sn satellites) for them at any temperature.
d) The ionic mechanism sketched above would be accelerated in a polar solvent. The amine
dissociation mechanism would probably not be affected.
e) Treatment of m-(Me
2
NCH
2
)
2
C
6
H
4
with BuLi. The coordination of the two amine arms would
automatically direct the metallation to the desired position. An alternative would be first making
1-Br-2,6-(Me
2
NCH
2
)
2
C
6
H
3
, but this might not be easy and would not have any advantage.
f) Monomeric ArLi would be Li
I
(OK), 6-e (not OK). It would probably dimerize via bridging
(3c-2e) aryl groups, after which the molecule would be coordinative saturated. Dimerization
would also allow formation of a near-tetrahedral (instead of planar) Li environment.
N
N
Li
N
N
Li

g) ArLi would do the normal addition of polar organometallics to carbonyl groups. The expected
product after hydrolysis is the alcohol (Ar)(C
6
H
5
)(CH
3
)COH. Side products could be: (1) the
starting ketone (ArLi acts as a base, deprotonates the ketone to the enolate, and after hydrolysis
the ketone is re-formed), and (2) Ar-Ar and/or [(C
6
H
5
)(CH
3
)COH]
2
(radical coupling, if radicals
would be involved in the addition). The latter possibility if not very likely since the ketone does
not have a very extended -system.
The Sn-C bond is much less polar than the Li-C bond, and the tin compound is also
coordinatively (over)saturated, so you expect a low reactivity. Probably, nothing will happen.
Treatment with acid might replace he acetate by the anion of the acid used, and acid might also
protonate the Me
2
N groups.