Organometallic chemistry I
Chapter 3: Organometallic Chemistry of Main Group Elements
Organometallic chemistry involves compounds with metal-carbon bonds (Mδ+—Cδ-).
VSEPR Theory and Its Utility
• VSEPR theory extends the Lewis model and predicts molecular shapes.
• Steps to Predict Molecular Shapes:
1. Draw the Lewis structure.
2. Count total bonds and lone pairs around the central atom.
3. Arrange pairs to minimize electron-electron repulsion.
▪ LP—LP repulsion > LP—BP repulsion > BP—BP repulsion.
4. Treat multiple bonds as a single bonding region.
• Steric Number (SN) = No. of attached atom + No. of lone pairs
o Maximizing the distance between steric numbers provides the most stable geometry.
• Molecular Shape vs. Geometry:
1. Shape: Ignore lone pairs (e.g., H2O = bent, NH3 = pyramidal).
2. Geometry: Consider both lone and bond pairs.
Bent’s Rule:
Electronegative substituents prefer orbitals with less s-character (more p-character),
while electropositive substituents prefer orbitals with more s-character.
• Application to CH₄, CF₄, and CH₂F₂:
o CH₄ and CF₄:
▪ Carbon uses four identical sp³ hybrids for bonding.
▪ Bond angles are approximately 109.5°.
o CH₂F₂:
▪ Hybrids are not identical due to different substituents.
▪ C-F bonds: Use sp3+x hybrids (more p-character, less s-character).
▪ C-H bonds: Use sp3-x hybrids (less p-character, more s-character).
• Effect on Bond Angles:
o Increased p-character in C-F bonds reduces the F-C-F bond angle.
o As p-character increases, the angle approaches 90°, typical of pure p-orbitals.
o In bond angle CF4 < CH2F2 < CH4.
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Organometallic chemistry I
Molecular shapes determined by VSEPR theory
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Organometallic chemistry I
Organometallic Compound Synthesis: General Methods of Preparation
1. Metal and Transmetallation Reactions:
o Reaction with Metal:
▪ Electropositive metal reacts with a halogen-substituted hydrocarbon:
2M +RX (alkyl or aryl) ⟶ MR +MX
Examples:
▪ 8Li + 4CH3 Cl ⟶ Li4 (CH3)4 + 4LiCl
Mg + CH3Br ⟶ CH3MgBr (organometal halide with Mg, Al, Zn)
o Transmetallation: A metal displaces another metal in an organometallic
compound: M +M′R ⟶ M′ +MR
▪ Examples: 2Ga + 3CH3 −Hg−CH3 ⟶ 3Hg + 2Ga (CH3)3
Transmetallation is favorable when the displacing metal is higher in the
electrochemical series than the displaced metal.
2. Metathesis:
o Reaction between an organometallic compound MR and a binary halide EX
MR +EX ⟶ ER +MX
• Examples: Li4 (CH3)4 +SiCl4 ⟶ 4 LiCl +Si (CH3)4
Al2 (CH3)6 + 2 BF3 ⟶ 2 AlF3 + 2B(CH3)3
Hydrocarbon groups bond to the more electronegative element.
Halogens bond to the more electropositive metal.
The halogen favors the formation of ionic compounds with the more electropositive
metal.
Alkyl and aryl groups tend to migrate from the less to the more electronegative
element.
When electronegativities are similar:
• Soft Element: Combines with organic groups.
• Hard Element: Bonds with fluoride or chloride.
Example:
• SnPh4(THF) + HgBr2(THF) ⟶ HgPhBr(s) + PhSnBr(THF)
• HgPhBr is insoluble in THF, influencing reaction outcome.
Redistribution Reactions:
• Occurs when the same central element is involved.
• Example: SiCl4 + SiMe4 ⟶ Me3SiCl + Me2SiCl2 + ⋅⋅⋅⋅
3 GeCl4 + 2 AlMe6 ⟶ 3 GeMe4 + 4 AlCl3
• Thermodynamic favorability based on metal electropositivity (e.g., Al > Ge).
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Organometallic chemistry I
3. Hydrometallation:
o Addition of a metal hydride to an alkene, producing an alkylmetal compound
EH +H2C=CH2 ⟶ E−CH2 −CH3
a. Hydroboration:
b. Hydrosilylation:
MeLi (Methyl Lithium):
• MeLi is generally handled in ether solution, while RLi compounds with longer chains
are soluble in hydrocarbons.
The best method would be
• Direct reaction: M +RX ⟶ MR (often contaminated with halide)
• Reaction with Organomercury Compounds: HgR2 + 2 Li ⟶ 2 LiR +Hg
Structure:
• In the solid state and solution, MeLi exists as a tetrahedral cluster.
• Higher homologs form hexamers or equilibrium mixtures of aggregates up to
hexamers in solution. Larger aggregates are broken down by Lewis bases like
TMEDA(Tetramethylethylenediamine).
Polylithiated Organic Molecules:
• Multiple lithium atoms per molecule are known in polylithiated organic molecules.
• Li2CH2, prepared by pyrolysis of MeLi, crystallizes in a distorted antifluorite structure,
where the finer details of the CH₂ group orientation are yet to be established.
• The antifluorite structure inverts the cation-anion positions compared to fluorite,
forming an FCC array of cations with tetrahedral holes filled by anions.
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