Classification of Organometallic compounds- based on the bonding feature
1.σ-bonded OM cpds :- contains M-C σ bonds
eg. M-Alkyl : RMgX,R2Zn,R3Pb,R3Al,R4Sn…..
M-Aryl : M-(C6H5)
2.π-bonded OM cpds
The TM binds to unsaturated HCs & their derivatives using their d-orbitals.
Here metal atom is bonded to L in such a way that donations electrons & back
acceptance by the L is feasible.
This category includes organometallic compounds of alkenes, alkynes &
some other C-containing compounds having electrons in their π
molecular orbitals,
The most important compound of this category is ferrocene or (bis-cyclopentadienyl)
iron, represented as (η5-C5H5)2Fe
It is known to have a ‘sandwitch’ structure
i. OM cpds with Cyclic π-donor
Examples
a. π-cyclopentadienyl ion complex
Ferrocene , bis(η5-cyclopentadienyl)iron(II), Fe(ή5-C5H5)2
b. Dibenzene chromium (π-complex)
Cr(ή6-C6H6)2
c. OM cpds with Cycloheptatriene, Cycloheptadiene, Cyclobutadiene,
cyclooctatetraene….
ii. OM cpds with Linear π –donor
Eg. Alkene complex (π –complex)
Zeise’s salt KPtCl3(ή2-C2H4) potasiumtrichloroethylene platinate(IV)
3. OM Complexes containing both σ &π bonding character
Metal carbonyl cpds formed b/n M & CO belong to this class.
i.Mononuclear carbonyls : contain one Metallic atom
per molecule
eg. Ni(CO)4, Fe(CO)5
ii. Polynuclear carbonyls : contains two or more metallic atoms per molecule
Eg. Mn2(CO)10, Fe2(CO)9, Fe3(CO)12…..
4. Organometallic compounds with multicentre bonds
Electron-deficient organometallic compounds occur in polymeric forms fall under
this category
Elements which have highest tendency to form this complex are Li, Be, Mg, B & Al.
Eg. [Al(CH3)3]2, (Li-CH3)4, [Be(CH3)2]n,, etc
Consider Al2Me6 which exists mostly as a dimer at RTP.
CH3
CH3 CH3
Al 750 Al 1230
CH3 CH3
CH3
The molecules are connected by two 3-centre-2-electron bonds
A 3c- 2e- bond is an electron-deficient chemical bond where 3 atoms share 2e-s.
The Al-C(terminal) & Al-C(bridging) distances are 1.97 and 2.14 Å, respectively.
Total number of available e-s are 12, but there are 8 covalent bonds
Structural features
i. 4CH3 terminal & 2CH3 bridging
ii. Al-CH3 terminal bond (1.96Ao) is shorter compared to Al-CH3 bridging bond (2.15Ao).
iii. CH3 (terminal)-Al-CH3 (terminal) bond angle 1200 whereas Al-CH3-Al bond angle
is 75o
Each Al has 3e- in three sp2 hybridized atomic orbital.
sp2 hybridized orbitals of Al overlap with sp3 hybridized orbitals of CH3.
Al-CH3 terminal bond is a 2 centre-2 electron bond.
The bridging bond is a 3 centre-2e-bond
5. Ionic organometallic compounds
Most of the organometallic compounds of alkali metals fall in this category
They have short life because of their high reactivity.
Eg, Na+(CH2=CH-CH2)-, Na+(CH2-C6H5)-,Na+(C6H5)-, Na+(C5H5)-, etc
Classification of Organometallic compounds- based on ligand type
1.M-alkenes
A. Zeise’s salt
The 1st OM cpds with the formula K[Pt(C2H4)Cl3].H2O
Synthesized in 1827 by Zeise, a Danish pharmacist
Alcoholic HCl
[PtCl4]2- + C2H4 [Pt(C2H4)Cl3] + Cl-
Pale yellow crystal
It was the first organometallic compound to
be isolated in pure form.
The Dewar-Chatt-Duncanson model explains the type of chemical bonding
between an unsaturated ligand & a metal forming a π complex.
The π-acid ligand donates electron density into a metal d-orbital from a π-
symmetry bonding orbital between the carbon atoms.
The metal donates electrons back from a filled t2g d-orbital into the empty π*
antibonding orbital of the ligand.
Both of these effects tend to reduce the C-C bond order, leading to an
elongated C-C distance and a lowering its vibrational frequency.
In the nickel compound Ni(CH2CH2)(PPh3)2 the C-C bond distance is 143 pm
(vs. 134pm for free ethylene).
The interaction can cause carbon atoms to "rehybridize“, for eg in metal
alkene complexes from sp2 towards sp3, which is indicated by the bending of
the hydrogen atoms on the ethylene back away from the metal.
Figure . Metal olefin bonding interactions.
The metal−olefin bonding interaction is best explained by the Dewar−Chatt model, that
takes into account two mutually opposing electron donation involving σ−donation of the
olefinic C=C π−electrons to an empty dπ metal orbital followed by π−back donation from
a filled metal dπ orbital into the unoccupied C=C π* orbital.
The extent of the C=C forward π-donation to the metal and the subsequent π−back
donation from the filled dπ orbital to the olefinic C=C π* orbital have a direct bearing on
the C=C bond of the metal bound olefinic moiety in form of bringing about a change in
hybridization as well as in the C−C bond distance (Figure below).
Figure . Metal olefin bonding
interactions.
Orbital interactions in a metal-ethylene complex.
A filled π-orbital on C2H4 An empty π-antibonding orbital on
overlaps with an empty d- C2H4 overlaps with a filled d-orbital
orbital on the metal. on the metal
If the metal to ligand π−back donation component is smaller than the ligand to metal
σ−donation, then the lengthening of the C−C bond in the metal bound olefin moiety is
observed. This happens primarily because of the fact that the alkene to metal σ−donation
removes the C=C π−electrons away from the C−C bond of the olefin moiety and towards
the metal center, thus, decreasing its bond order and increasing the C−C bond length.
Additionally, as the metal to ligand π−back donation increases, the electron donation of
the filled metal dπ orbital on to the π* orbital of the metal bound olefin moiety is enhanced.
This results in an increase in the C−C bond length. The lengthening of the C−C bond in
metal bound olefin complex can be correlated to the π−basicity of the metal.
For example, for a weak π−basic metal, the C−C bond lengthening is anticipated to be
small while for a strong π−basic metal, the C−C lengthening would be significant.
Structural features of Zeise’s salt
i. Pt2+ ion is a 4-coordinated, with 3 sites occupied by the Cl- & the 4th site by the
ethylene molecule
ii. Its geometry is square planar
iii. The π-electrons in ethylene are coordinated to the Pt metal.
Overlap of the π-bonding orbital of the alkene with a vacant σ-type orbital of the
Pt produces L→M bond of σ-type.
In addition ,a π-bond originating from the overlap of a filled orbital of Pt atom with
the empty π-bonding orbital of the alkenes is formed.
so, Ethylene molecule is called a π-bonding ligand.
iv. The length of the coordinated alkene C-C bond (1.375A◦ ) > the C=C bond
length (1.337A◦ ) in the free ethylene molecule.
v. The originally planar ethylene becomes non-planar on bonding itself to Pt.
vi. The metal is located above the plane of the alkene, symmetrically b/n the two
skeletal carbon atoms.
vii. The C=C bond is perpendicular to the molecular plane.
Viii. The two carbon atoms are almost equidistant ( non-bonded distance) from the Pt
ion.
ix. Back-bonding is also indicated by a bending of the four hydrogen atoms away
from the Pt atom.
x. The water molecule is not attached to the metal but is accommodated in the
lattice as a solvent molecule of crystallization.
In 1954, crystal structure determination by X-ray method, IR and Raman spectral
data solved the structure.
Olefin binding strength is very sensitive to steric changes:
ethylene > propylene > cis-2-butene > trans-2-butene
Chelating dienes form more stable complexes than simple alkenes
B. Rhodium-Ethene complex
CH2 CH CH CH2
RhCl3(aq) + C2H4 Cl
Rh Rh
CH2 Cl CH CH2
CH
Other M-alkene complexes
Several other alkenes similarly form complexes with metals, such as Pt,Fe,Cr etc.
Very stable complexes are formed when the ligand is a diolefin.
Metal alkenes complexes are synthesized by the following methods
Bicyclo [2,2,1] hepta-2,5-diene rhodiym(I)chloride dimer
Reactions of metal alkenes
1. Insertion
commonly displayed by alkenes as they insert into M−X bonds yielding metal alkyls.
The rxn occurs readily at RT for X = H, whereas for other elements ,such insertions become rare.
The strained alkenes & alkynes undergo such insertion readily.
PtHCl(PEt3)2 + C2H4 ↔ PtEtCl(PEt3)2
2. Nucleophilic attack
3. Oxidative addition
Alkenes containing allylic
hydrogens undergo oxidative
addition to give a allyl hydride
complex.
2. Metal-Alkynes
Alkynes behave in ways broadly similar to alkenes, but being more EN, they tend
to encourage back donation and bind more strongly.
The substituents tend to fold back away from the metal by 30 ◦–40◦ in the complex,
& the M−C distances are slightly shorter than in the corresponding alkene
complexes.
Why are alkynes more electronegative than alkenes?
Upon complexation, the C-C bond elongates & weakening of the C-C bond and the
alkynyl carbon bends..
confirmed by IR
η2-coordination to a single metal center
When bonded side-on to a single metal atom, an alkyne serves as a dihapto
usually 2e- donor.
For early metal complexes, e.g., Cp2Ti(C2R2), strong π-back bonding into one of
the π* antibonding orbitals of the alkyne is indicated.
For late transition metal complexes, e.g., Pt(PPh3)2(MeC2Ph), the π-back bonding
is less prominent, and the complex is assigned oxidation state (0).
Alkynes can also form complexes that appear to be coordinatively unsaturated
Coordinatively unsaturated
metal alkynes
In such cases the alkyne also donates its second C=C π-bonding orbital, which
lies at right angles to the first.
In some complexes, the alkyne is classified as a 4e- donor. In these cases, both pairs of
π-electrons donate to the metal. This kind of bonding was first implicated in complexes of
the type W(CO)(R2C2)3
i.e.The alkyne is now a 4e donor.
η2, η2-coordination
bridging two metal
centers
Because alkynes have two π bonds, alkynes can form stable complexes in
which they bridge two metal centers. The alkyne donates a total of four
electrons, with two electrons donated to each of the metals.
Eg. η2-diphenylacetylene-(hexacarbonyl)dicobalt(0)
Alkynes readily bridge a M−M bond, in which case they can act as conventional
2e- donors to each metal.
END OF SESSION-3
