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Org A No Met PDF
Gerken Page195
16. Organometallics
We now move on to consider transition-metal organometallic compounds. Organometallic compounds are compounds that
contain a metal-carbon bond. Organic derivatives of the main-group metals were well known by the turn of the century.
Examples include alkyl lead and zinc compounds and, of course, Grignard reagents. All attempts to make analogous σ-bonded
alkyl derivatives with transition metals failed miserably. We now know why they failed, and today there are such derivatives, but
they are not the most common organometallics.
Carbonyl ligands can also cap a trigonal face formed by three metal centres, hence bridging three metal atoms. This time the lone
pair is shared by three metal centres.
hν
2 Fe(CO)5 → CO + Fe2(CO)9
HOAc
orange solid 90% yield,
m.p. 100 °C
Bond strength is given simply be Hooke’s law: ν(CO) = 1/(2πc) (kCO/µCO)1/2, where kCO is the force constant for the bond
and µCO is the reduced mass. This law fits nicely the range of organic CO bond types, and also can be used to advantage in metal
carbonyls. For example, we might expect the extent of synergistic bonding to increase with increasing charge on the metal. This
is seen in the series:
Mn(CO)6+ 2090 cm-1; Cr(CO)6 1990 cm-1; V(CO)6- 1860 cm-1
If we look back at the table of example binary carbonyls, we see that there are some CO’s which bridge between two metal
centres. In this bonding mode, the ligand acts as a 2-electron donor, and is formally a formaldehyde diradical. This means that
each metal receives only one electron. In some other complexes, CO exist as a triply bridging ligand, capping a trigonal face of
metal atoms, as in [Cp4Fe4(CO)4], in which the faces of the tetrahedron of iron atoms, each connected to a terminal Cp ligand, is
capped with CO ligands. This makes CO a derivative with an sp3 hybridized carbon.
Clearly the shift in the ν(CO) follow the predicted bond-order changes using such very simplistic arguments. There is a large
range within each group, which is readily explained by the wide variety of metal centres and charges involved.
The aromatic 6π systems are the most common, and cyclopentadienyl complexes are by far the most abundant of these. However,
transition-metal complexes of anti-aromatic rings are also well known, and in fact cylcobutadiene was first isolated as a
coordination complex.
10.2 Hapticity
An organic ligand can coordinate to one metal centre
via one, two, three or more carbon atoms; such ligands are
characterized by their hapticity, which gives the number of
atoms of one ligand in approximately the same distance
from the transition metal. Such ligands are labelled as
monohapto, dihapto, trihapto, etc. and its hapticity is
denoted using η (eta, superscript: number of coordinated
ligand atoms) in front of a ligand: η1, η2, η3, η4, η5, etc.
Cyclopentadienyl (C5H5- = Cp) acts as a monohapto,
trihapto, and pentahapto ligand:
This may occur in situ by converting a metal diene complex into a Cp complex, but more usually is done beforehand using an
active metal. Thus NaC5H5 and TlC5H5 are common synthetic sources of Cp-. Examples are:
2NaCp + FeCl2 → Cp2Fe (ferrocene) + 2NaCl
TlCp + Mn(CO)5Cl → CpMn(CO)3 + TlCl + 2CO
MoCl5 + 3NaCp + 2NaBH4 → Cp2MoH2 + 5NaCl + B2H6 + C5H5-
In the lab (exp #10), the cyclopentadienide anion is generated from cylcopentadiene and KOH. There are some rare examples of
other synthetic routes, including nucleophilic displacement:
This example contains an η1-Cp and the more common η5-Cp coordination modes.
Chemistry 3820 Lecture Notes Dr. M. Gerken Page200
and to the hydrogens are irrelevant, and are omitted from this
discussion.
Step 1: Form the Cp SAO’s into sets of SAO’s for the Cp2
arrangement, in eclipsed geometry.
a”2 → a1’ + a2”
e1’ → e1” + e1’
e2” → e2’ + e2”
Step 2: Order these by the number of nodes they have.
Step 3: Allow them to interact with metal orbitals of suitable
symmetry. (from the character tables or from visual inspection).
Reactions:
Ferrocene has a vast organic chemistry because it is sufficiently stable to survive the reaction conditions required for
electrophilic aromatic substitution. A typical reaction involving the aromatic ligand in ferrocene is the Friedel-Crafts acylation
(experiment #11 from the lab): AlCl3
CH3COCl + Fe(η5-C5H5)2 → Fe(η5-C5H5)(η5-C5H4COCH3) + HCl
The salt of the latter, K[(η2-C2H4)PtCl3]·H2O, is known as Zeise’s salt. Zeise first prepared these interesting and prototypical
complexes in 1827, making these the oldest known transition-metal organometallic compounds! However, he originally
formulated them as KCl·PtCl2·C2H5OH and the true nature of this complex was discovered only in the 1950’s.
The orientation of the alkene fragment in these and similar complexes suggests that the π HOMO of the alkene acts as a σ-
donor to the metal. However, it has since been shown that alkenes also bond lower-valent metals, for example Pt and Ni in the
zero-valent state bond to four double bonds of two cyclic diene ligands, i.e., COD – cylcooctadiene:
Note that in this complex the centres of the double bonds form a tetrahedral arrangement, consistent with d10, rather than the
square-planar geometry of Zeise’s salt, which contais a d8-transition-metal centre. Such complexes of zero-valent metals suggest
that alkenes can have π-acceptor as well as σ-donor properties. This can be rationalized using the MO description of ethene,
which has both, a π bonding MO and a π* antibonding MO (see below).
Another important class of zero-valent metal complexes of alkenes contains the Ni, Pd, and Pt(0) complexes of the type:
faces are distinguished, which can be of importance in catalytic sequences involving optical activity introduced during the
reaction involving an alkene. The alkene π* orbital is polarized away from the region between the C atoms, making it perfectly
adapted to interact with the filled metal d orbital. It thus acts as a π acceptor.
We can explain the structural parameters discussed above in terms of this model. With Pt(II), the metal is relatively electron
poor, so that ethylene coordinates mostly as an electron donor, and the extent of back-bonding is not so significant. Since back-
bonding fills the π* orbital, lengthening of the C-C bond is expected. The bend-back of the R groups, in this case H, is explained
by partial rehybridization towards sp3 at C.
In Pt(0) complexes, the metal is much more electron-rich causing much more extensive π back-bonding. Thus the C-C bond
is lengthened more and the rehybridization is greater.
When a strong electron-withdrawing group is used on the alkene, the π-acceptor character of the ligand is increased, and the
extent of back-bonding becomes extreme, with very long C-C bonds and extensive bend-back of the R groups. In the limit, this
forms a metallacyclopropane complex:
The limit of back-bonding: metallacyclopropane: here the C-C bond is a single bond and the C atoms
are sp3 hybridized.
M