-- 1 --

CHEM4680 - Organometallic Chemistry

Mid-term test: electron counting, main group metals and NMR
Rough answers
1. Counting (48 marks).

Fe
OC
OC CO
a
Fe = 8
C
4
H
4
= 4
3*CO = 6
tot 18
Fe
(0)
if you count C
4
H
4
as neutral (cyclobutadiene).
But assuming C
4
H
4
2-
or C
4
H
4
2+
is also legal, and
would lead to Fe
II
or Fe
-II
.
Stable complex, antiaromatic C
4
H
4
stabilized by
coordination to Fe.
Mo
O
O
N
O
b

Mo = 6
2*O- = 2
O= = 2
N= = 2
tot 12
Additional lone pairs on
alkoxide, oxo and imido
ligands could contribute.
Mo
VI
: 1- on each alkoxide, 2-
on both oxo and imido ligands.
Unsaturated, but crowded, and
the extra lone pairs could
provide stabilization. Exists
but is reactive.

N
Fe N
N
N
N
N
2+
Fe(Terpy)
2
2+
c

Fe = 8
6*N = 12
2+= -2
tot 18
Fe
II
(b/c total charge)
Saturated and stable.

-- 2 --
Me
Mg Mg
Me
O
Br
O
Br
d

Mg = 2
Br = 1
THF = 2
Me- = 1
Me-Mg (3c2e) =2
tot 8
Mg
II

Each Me counts for 1e towards
only one of the Mg atoms! To
the other Mg, the Mg-Me bond
is a 2e donor.
Saturated. Because Mg
compounds are highly ionic, a
higher CN and count would
also be possible.

Br
Mg Mg
Br
O
Me
O
Me
e

Mg = 2
Me = 1
Br- = 1
Br = 2
THF = 2
tot 8
Mg
II

Each Br is a 1e-donor to one
Mg and 2e to the other.
Saturated. Because Mg
compounds are highly ionic, a
higher CN and count would
also be possible.

Mo Mo
CO
OC
CO
CO
OC
OC
f

Mo = 6
Cp = 5
3*CO = 6
Mo- = 1
tot = 18
Mo
I
(b/c of the Cp
-
).
Note that the Mo-Mo bond does
not count for the oxidation
state!
Saturated and stable

g The Me-bridged situation should be less stable than the Br-bridged situation. The Me
bridge is a 3c2e situation, where one electron pair is shared by the Me group and two Mg
atoms. The bridging Br forms a "covalent" bond to one Mg but uses a different electron
pair to donate to the second Mg.
h If each Mo loses a CO ligand, it becomes 16e. To get back
to 18e, it needs to form two additional Mo-Mo bonds (each
counting for 1e for each Mo). This produces the complex
shown at the right. What happens in reality is slightly more
complicated ("semi-bridging CO").
Mo Mo
OC
CO
CO
OC
-- 3 --
2. Main group metals (30 marks)
a In the absence of a catalyst, this is just the reaction of a Grignard with an ester. The
obvious products are a ketone and an alkoxide (which on hydrolysis gives an alcohol).
Reduction via -hydrogen transfer is not possible because the alkyl on Mg does not have a -
H. One-electron transfer is a possibility, but not very likely because this is not a very
extended conjugated system. One possibility not covered in class would be group transfer
polymerization similar to that of acrylates.
R
COOEt
MeMgCl
1
R
O
Me
MeMgCl
R
Me
OMgCl
Me
R
Me
OH
Me
H
+
, H
2
O

Main-group metal compounds tend not to do "conjugate addition", which is why Ma's
reaction uses a catalyst.
b The transfer of Me groups from the Grignard to Fe must be faster (more than 20 times
faster, in fact) than the direct transfer to 1 (uncatalyzed reaction), else you would mainly get
the products of the uncatalyzed reaction.
c Complex 2, as shown in the question, would be 4e and two-coordinate around Mg; it
is clearly unsaturated. Intramolecular coordination to the oxygen atom of the OEt group is
possible but still leaves an unsaturated complex. One would expect at least a dimer via
bridging alkoxide oxygens (these oxygens have the highest negative charge and hence the
largest tendency to bridge) or bridging chlorides. Alternatively, since this is formally an
enolate, one could have the ligand bridging via both C and O atoms; this is in fact what
happens with less electropositive elements like Zn. For the highly ionic Mg complex, the O-
bridged complex is more likely, also because in the C,O-bridged structure the ester
coordination cannot be maintained. Of course, the C,O-bridged dimer show below could still
polymerize via bridging chlorides to form a saturated structure.
Me
R O
OEt
Mg
Me
R O
EtO
Mg
Cl
Cl
Me
R O
OEt
Mg
Me
R O
EtO
Mg
Cl
Cl
Me
R
O
EtO
Mg
Mg
Me
R
O
EtO
Cl
Cl

-- 4 --
3. NMR (20 marks)
a Structure 3b has a twofold rotation axis passing through the metal atom and between
the chlorides and the P atoms. It would therefore have equivalent P atoms, should show a
singlet in
31
P and is not compatible with the observed low-temperature spectrum. Structure 3a
has no symmetry, the P atoms are inequivalent (one trans to O, one trans to Cl), and this
structure would be compatible (this was confirmed by an Xray structure of the complex).
b Clearly, the two P atoms have become equivalent "on the NMR timescale", that is,
they see on average the same chemical environment. Assume that at low temperature the P
atoms are not equivalent (e.g. in 3a), there are two possibilities: (1) a mechanism that
exchanges the two P atoms, but still has 3a as the prevalent structure, or (2) a shifting of the
equilibrium from 3a to 3b. Strong temperature-dependence of the equilibrium would only be
expected if there is a strong entropic driving force, such as a change in number of particles,
which is not the case here, so (1) is more likely.
Octahedral environments do not easily rearrange, so the most likely mechanism is detachment
of one of the groups from the metal, rearrangement in the 5-coordinate intermediate, and then
re-coordination of the detached group. Which group would detach most easily? Phosphine
coordination to early transition metals is generally weak, so P would be a good candidate. In a
polar solvent (the question does not mention a solvent) Cl, dissociating as Cl
-
, is also a
reasonable choice. Dissociation of the phenolate oxygen is the least likely: phenoxide is a
much poorer leaving group than chloride in general, and in the present case the phenoxide
coordination is stabilized by the chelate effect.
P
Hf
O
Cl
P
Cl
O
O
Hf
P
Cl
O
Cl
P
P
Hf
O
Cl
Cl
O
P
O
Hf
Cl
O
Cl
P
P

Note that the P and O atoms do not have to physically exchange places: each P just has to go
to a position that is equivalent to where the other P was in the original structure.