Hapticity

In

• Ferrocene: bis(η⁵-cyclopentadienyl)iron
• Uranocene: bis(η⁸-1,3,5,7-cyclooctatetraene)uranium
• W(CO)₃(PPrⁱ₃)₂(η²-H₂): the first compound to be synthesized with a dihydrogen ligand.^[8][9]
• IrCl(CO)[P(C₆H₅)₃]₂(η²-O₂): the
  dioxygen derivative which forms reversibly upon oxygenation of Vaska's complex
  .

• Side-on bonding of molecules containing σ-bonds like H₂:
  • W(CO)₃(PⁱPr₃)₂(η²-H₂)^[8][9]
• Side-on bonded ligands containing multiple bonded atoms, e.g.
  fullerene
  , which is bonded through donation of the π-bonding electrons:
  • K[PtCl₃(η²-C₂H₄)]^.H₂O
• Related complexes containing bridging π-ligands:
  • (μ-η²:η²-
    Cp*₂Sm)₂(μ-η²:η²-N₂)^[10]
  • Dioxygen
    in bis{(trispyrazolylborato)copper(II)}(μ-η²:η²-O₂),

Note that with some bridging ligands, an alternative bridging mode is observed, e.g. κ¹,κ¹, like in (Me₃SiCH₂)₃V(μ-N₂-κ¹(N),κ¹(N′))V(CH₂SiMe₃)₃ contains a bridging dinitrogen molecule, where the molecule is end-on coordinated to the two metal centers (see hapticity vs. denticity).

• The bonding of π-bonded species can be extended over several atoms, e.g. in
  allyl, butadiene ligands, but also in cyclopentadienyl or benzene
  rings can share their electrons.
• Apparent violations of the 18-electron rule sometimes are explicable in compounds with unusual hapticities:
  • The 18-VE complex (η⁵-C₅H₅)Fe(η¹-C₅H₅)(CO)₂ contains one η⁵ bonded cyclopentadienyl, and one η¹ bonded cyclopentadienyl.
  • Reduction of the 18-VE compound [Ru(η⁶-C₆Me₆)₂]²⁺ (where both aromatic rings are bonded in an η⁶-coordination), results in another 18-VE compound: [Ru(η⁶-C₆Me₆)(η⁴-C₆Me₆)].
• Examples of polyhapto coordinated heterocyclic and inorganic rings: Cr(η⁵-C₄H₄S)(CO)₃ contains the sulfur heterocycle thiophene and Cr(η⁶-B₃N₃Me₆)(CO)₃ contains a coordinated inorganic ring (B₃N₃ ring).

Electrons donated by "π-ligands" versus hapticity

Changes in hapticity

The hapticity of a ligand can change in the course of a reaction.^[12] E.g. in a redox reaction:

Here one of the η⁶-benzene rings changes to a η⁴-benzene.

Similarly hapticity can change during a substitution reaction:

Here the η⁵-cyclopentadienyl changes to an η³-cyclopentadienyl, giving room on the metal for an extra 2-electron donating ligand 'L'. Removal of one molecule of CO and again donation of two more electrons by the cyclopentadienyl ligand restores the η⁵-cyclopentadienyl. The so-called

Hapticity vs. denticity

Hapticity must be distinguished from

Molecules with polyhapto ligands are often fluxional, also known as stereochemically non-rigid. Two classes of fluxionality are prevalent for organometallic complexes of polyhapto ligands:

• Case 1, typically: when the hapticity value is less than the number of sp² carbon atoms. In such situations, the metal will often migrate from carbon to carbon, maintaining the same net hapticity. The η¹-C₅H₅ ligand in (η⁵-C₅H₅)Fe( η¹-C₅H₅)(CO)₂ rearranges rapidly in solution such that Fe binds alternatingly to each carbon atom in the η¹-C₅H₅ ligand. This reaction is
  sigmatropic rearrangement.^{[citation needed]} A related example is Bis(cyclooctatetraene)iron
  , in which the η⁴- and η⁶-C₈H₈ rings interconvert.
• Case 2, typically: complexes containing cyclic polyhapto ligands with maximized hapticity. Such ligands tend to rotate. A famous example is
  principal axis of the molecule that "skewers" each ring (see rotational symmetry
  ). This "ring torsion" explains, inter alia, why only one isomer can be isolated for Fe(η⁵-C₅H₄Br)₂ since the torsional barrier is very low.