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Organometallic Chemistry and Homogeneous Catalysis 1, RBB

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Background

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Historical use of transition metal catalysts

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Sabatier-Senderens process

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  • CO + H2 → C1 - C30 alkanes and alkenes
  • heterogeneous Co or Fe catalysts

Mechanistic aspects of homogeneous catalysis

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Ligand effects

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Electronic effects

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Steric effects

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Ligand association and dissociation

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Migratory insertion and elimination

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Lutetium hydride catalysis

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precatalyst name mol prod. / mol cat.
RhCl(PPh3)3 Wilkinson's catalyst 650
[Rh(COD)(PPh3)2]+ Osborn's catalyst 4000
[Ir(COD)(py)(PCy3)]+ Crabtree's catalyst 6500
(Cp*2LuH)2 ? 120000
  • Lu(III) is hard and very electropositive
  • Does not undergo oxidative addition of H2 to form Lu(V)H2
  • Lanthanide contraction makes it very hard to remove electrons from Lu(III)
  • Impractical due to extreme air and moisture sensitivity...
  • ...but it may be possible to get the same mechanism with titanocene catalysts

Alkene oxidation – the Wacker process

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Heterogeneous catalysis

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Modern homogeneous catalysis

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Co-catalyst: methylaluminoxane

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Specific applications

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Step 3: metathesis

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Others to sort

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