Organometallic Chemistry and Catalysis

50 lessons, pages 3736–3785.

  1. What Is Organometallic Chemistry? — Metal–carbon bonds, homogeneous catalysts and scope of the field
  2. Classifying Ligands: L, X and Z Types — Electron donation and formal ligand classification in organometallic complexes
  3. Hapticity and Denticity — η notation for π ligands versus donor-atom count for chelating ligands
  4. Electron Counting by Two Methods — Ionic and covalent methods for total valence electron counts
  5. The 18-Electron Rule — Valence-shell filling, useful predictions and common limitations
  6. Exceptions to the 18-Electron Rule — Square-planar d8 complexes, early metals and steric constraints
  7. Oxidation States and d-Electron Counts — Formal charges, metal groups and electron-count consistency
  8. Geometry and Coordination Environment — Square-planar, tetrahedral and octahedral organometallic structures
  9. Phosphine Ligands: Sterics and Electronics — Cone angle, donor strength and catalyst behaviour
  10. Metal Carbonyl Bonding — Carbon monoxide σ donation and π back-donation
  11. Carbonyl Infrared Spectroscopy — Using ν(CO) to assess metal–CO back-bonding
  12. Alkene and Alkyne Complexes — Dewar–Chatt–Duncanson bonding and activation of π ligands
  13. Metal Hydrides — Hydride ligands, bonding and their roles in catalytic hydrogen transfer
  14. Metal Alkyls and β-Hydrogen Stability — Metal–carbon σ bonds and structural requirements for β-hydride elimination
  15. Metal Carbenes and Carbynes — Fischer- and Schrock-type carbon ligands and their reactivity
  16. Oxidative Addition: Electron and Oxidation Accounting — Formal oxidation-state increase and coordination-number change
  17. Oxidative Addition Mechanisms — Concerted, ionic and radical pathways for bond activation
  18. Reductive Elimination — Bond formation from two cis ligands and catalyst regeneration
  19. Carbon Monoxide Migratory Insertion — Conversion of metal alkyl and CO ligands into an acyl complex
  20. Alkene Insertion into Metal–Hydrogen and Metal–Carbon Bonds — Hydrometallation and chain-growth insertion steps
  21. β-Hydride Elimination — Syn-coplanar geometry, vacant sites and alkene formation
  22. Ligand Substitution and Coordination Vacancies — Creating open sites for substrate binding and catalytic turnover
  23. Associative and Dissociative Substitution — Kinetic signatures and electron-count implications
  24. Transmetallation — Transfer of an organic group between metals in coupling cycles
  25. σ-Bond Metathesis — Four-centre exchange at metals that avoid oxidative addition
  26. C–H Activation — Routes to metal–carbon bonds from normally inert C–H bonds
  27. Catalytic Cycles and Turnover — Reading elementary steps, net reactions and turnover numbers
  28. Oxidative Addition and Reductive Elimination in a Cycle — Balancing complementary bond-breaking and bond-forming steps
  29. Hydroformylation of Alkenes — Rhodium- or cobalt-catalysed addition of CO and H₂
  30. Homogeneous Alkene Hydrogenation — Coordination, H₂ activation and hydride transfer in a catalytic cycle
  31. Asymmetric Hydrogenation — Chiral ligands and enantioselective product formation
  32. Cross-Coupling: Shared Catalytic Logic — Oxidative addition, transmetallation and reductive elimination
  33. Suzuki–Miyaura Coupling — Organoboron reagents, base activation and C–C bond formation
  34. Heck Coupling — Palladium-catalysed arylation of alkenes and β-hydride elimination
  35. Negishi, Kumada and Stille Couplings — Comparing organozinc, organomagnesium and organotin partners
  36. Buchwald–Hartwig Amination — Palladium-catalysed formation of aryl–nitrogen bonds
  37. Olefin Metathesis: The Net Reaction — Exchange of alkene fragments and driving forces
  38. Olefin Metathesis Mechanism — Metal alkylidenes, metallacyclobutanes and cycloreversion
  39. Wacker Oxidation — Palladium-mediated conversion of ethene to acetaldehyde
  40. Coordination Polymerisation of Ethene — Repeated alkene insertion at a metal–carbon bond
  41. Ziegler–Natta and Metallocene Catalysts — Active-site control of chain growth and tacticity
  42. Catalytic Carbonylation — CO insertion and carbonyl-containing product synthesis
  43. Homogeneous and Heterogeneous Catalysts Compared — Soluble molecular sites versus surfaces and separability
  44. Supported Molecular Catalysts — Immobilisation strategies, leaching and site accessibility
  45. Thermodynamics and Kinetics of Catalytic Steps — Free-energy profiles, resting states and reversible elementary reactions
  46. Resting States and Turnover-Limiting Steps — Distinguishing abundant intermediates from slow or controlling steps
  47. Chemoselectivity, Regioselectivity and Stereoselectivity — How ligands and conditions direct catalytic products
  48. Catalyst Deactivation and Recyclability — Aggregation, poisoning, ligand loss and recovery strategies
  49. Mechanistic Tools for Organometallic Catalysis — Spectroscopy, kinetics, isotope effects and intermediate trapping
  50. Organometallic Chemistry and Catalysis: Unit Review — Electron counting, elementary steps and catalytic-cycle reasoning