Hapticity

Ferrocene contains two η⁵-cyclopentadienyl ligands

Hapticity is the coordination of a ligand to a metal center via an uninterrupted and contiguous series of atoms.^[1] The hapticity of a ligand is described with the Greek letter η ('eta'). For example, η² describes a ligand that coordinates through 2 contiguous atoms. In general the η-notation only applies when multiple atoms are coordinated (otherwise the κ-notation is used). In addition, if the ligand coordinates through multiple atoms that are not contiguous then this is considered denticity ^[2] (not hapticity), and the κ-notation is used once again.^[3] When naming complexes care should be taken not to confuse η with μ ('mu'), which relates to bridging ligands.^[4][5]

History

The need for additional nomenclature for organometallic compounds became apparent in the mid-1950s when Dunitz, Orgel, and Rich described the structure of the "sandwich complex" ferrocene by X-ray crystallography^[6] where an iron atom is "sandwiched" between two parallel cyclopentadienyl rings. Cotton later proposed the term hapticity derived from the adjectival prefix hapto (from the Greek haptein, to fasten, denoting contact or combination) placed before the name of the olefin,^[7] where the Greek letter η (eta) is used to denote the number of contiguous atoms of a ligand that bind to a metal center. The term is usually employed to refer to ligands containing extended π-systems or where agostic bonding is not obvious from the formula.

Historically important compounds where the ligands are described with hapticity

• 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.

Examples

The η-notation is encountered in many co-ordination compounds:

• 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. ethylene in Zeise's salt or with 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-C₂H₂)Co₂(CO)₆ and (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 18VE 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" vs. hapticity

Ligand	Electrons contributed (neutral counting)	Electrons contributed (ionic counting)
η^1 Allyl	1	2
η^3-Allyl cyclopropenyl	3	4
η^3-Allenyl	3	4
η^2-Butadiene	2	2
η^4-Butadiene	4	4
η^1-cyclopentadienyl	1	2
η^3-cyclopentadienyl	3	4
η^5-cyclopentadienyl pentadienyl cyclohexadienyl	5	6
η^2-Benzene	2	2
η^4-Benzene	4	4
η^6-Benzene	6	6
η^7-Cycloheptatrienyl	7	6
η^8-Cyclooctatetraenyl	8	10

Changes in hapticity

The hapticity of a ligand can change in the course of a reaction.^[11] 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 indenyl effect also describes changes in hapticity in a substitution reaction.

Hapticity vs. denticity

Hapticity must be distinguished from denticity. Polydentate ligands coordinate via multiple coordination sites within the ligand. In this case the coordinating atoms are identified using the κ-notation, as for example seen in coordination of 1,2-bis(diphenylphosphino)ethane (Ph₂PCH₂CH₂PPh₂), to NiCl₂ as dichloro[ethane-1,2-diylbis(diphenylphosphane)-κ²P]nickel(II). If the coordinating atoms are contiguous (connected to each other), the η-notation is used, as e.g. in titanocene dichloride: dichlorobis(η⁵-2,4-cyclopentadien-1-yl)titanium.^[12]

Hapticity and fluxionality

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 degenerate and, in the jargon of organic chemistry, it is an example of a sigmatropic rearrangement. 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 ferrocene, Fe(η⁵-C₅H₅)₂, wherein the Cp rings rotate with a low energy barrier about the principal axis of the molecule that "skewers" each ring (see rotational symmetry). This "ring whizzing" explains, inter alia, why only one isomer can be isolated for Fe(η⁵-C₅H₄Br)₂. In this case, the rotamers are not necessarily degenerate, but the rotational barriers have low energies of activation.

References

1. "IUPAC Gold Book - η (eta or hapto) in inorganic nomenclature". Goldbook.iupac.org. 2014-02-24. Retrieved 2016-01-18.
2. "IUPAC Gold Book - denticity". Goldbook.iupac.org. 2014-02-24. Retrieved 2016-01-18.
3. "IUPAC Gold Book - κ (kappa) in inorganic nomenclature". Goldbook.iupac.org. 2014-02-24. Retrieved 2016-01-18.
4. "IUPAC Gold Book - bridging ligand". Goldbook.iupac.org. 2014-02-24. Retrieved 2016-01-18.
5. "IUPAC Gold Book - µ- (mu) in inorganic nomenclature". Goldbook.iupac.org. 2014-02-24. Retrieved 2016-01-18.
6. J. Dunitz, L. Orgel, A. Rich (1956). "The crystal structure of ferrocene". Acta Crystallographica 9 (4): 373–5. doi:10.1107/S0365110X56001091.
7. F. A. Cotton (1968). "Proposed nomenclature for olefin-metal and other organometallic complexes". J. Am. Chem. Soc. 90 (22): 6230–6232. doi:10.1021/ja01024a059.
8. Kubas, Gregory J. (March 1988). "Molecular hydrogen complexes: coordination of a σ bond to transition metals". Accounts of Chemical Research 21 (3): 120–128. doi:10.1021/ar00147a005.
9. Kubas, Gregory J. (2001). Metal Dihydrogen and σ-Bond Complexes - Structure, Theory, and Reactivity (1 ed.). New York: Kluwer Academic/Plenum Publishers. ISBN 978-0-306-46465-2. LCCN 00059283.
10. D. Sutton (1993). "Organometallic diazo compounds". Chem. Rev. 93 (3): 995–1022. doi:10.1021/cr00019a008.
11. Huttner, Gottfried; Lange, Siegfried; Fischer, Ernst O. (1971). "Molecular Structure of Bis(Hexamethylbenzene)-Ruthenium(0)". Angewandte Chemie International Edition in English 10 (8): 556–557. doi:10.1002/anie.197105561.
12. "IR-9.2.4.1 Coordination Compounds: Describing the Constitution of Coordination Compounds: Specifying donor atoms: General" (PDF). Nomenclature of Inorganic Chemistry – Recommendations 1990 (the 'Red Book') (Draft March 2004 ed.). IUPAC. 2004. p. 16.