Zeise's salt

Zeise's salt[1]
IUPAC name

Potassium trichloro(ethene)platinate(II)
Identifiers
CAS number 16405-35-9
PubChem 16211684
Properties
Molecular formula C2H4Cl3KPt
Molar mass 368.59 g mol−1
Hazards
EU classification Xi
R-phrases R36/37/38
S-phrases S26-S37/39
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Except where noted otherwise, data are given for materials in their standard state (at 25 °C, 100 kPa)
Infobox references

Zeise's salt, potassium trichloro(ethene)platinate(II), is the chemical compound with the formula K[PtCl3(C2H4)]·H2O. The anion of this air-stable, yellow, coordination complex contains an η2-ethylene ligand. The anion features a platinum atom with a square planar geometry.

Contents

Preparation

This compound is commercially available as a hydrate. The hydrate is commonly prepared from K2[PtCl4] and ethylene in the presence of a catalytic amount of SnCl2. The water of hydration can be removed in vacuo.[2]

Structure

In Zeise's salt and related compounds, the alkene rotates about the metal-alkene bond with a modest activation energy. Analysis of the barrier heights indicates that the π-bonding between most metals and the alkene is weaker than the σ-bonding. In Zeise's anion, this rotational barrier cannot be assessed by NMR spectroscopy because all four protons are equivalent. Lower symmetry complexes of ethylene, e.g. CpRh(C2H4)2, are, however, suitable for analysis of the rotational barriers associated with the metal-ethylene bond.[3]

History

Zeise's salt was one of the first organometallic compounds to be reported.[4] Its inventor W. C. Zeise, a professor at the University of Copenhagen, prepared this compound in 1820s while investigating the reaction of PtCl4 with boiling ethanol, and proposed that the resulting compound contained ethylene. Justus von Liebig, an influential chemist of that era, often criticised Zeise's proposal, but Zeise's theories were decisively supported in 1868 when Birnbaum prepared the complex using ethylene.[5][6]

Zeise's salt received a great deal of attention during the second half of the 19th century because chemists could not properly explain the molecular structure of the salt. This question remained unanswered until the advent of x-ray diffraction in the 20th century.[7]

Zeise's salt stimulated much scientific research in the field of organometallic chemistry, and would be key in defining new concepts in chemistry such as Hapticity. The Dewar-Chatt-Duncanson model explains how the metal is coordinated to the double bond.

Related compounds

Many other ethylene complexes have been prepared. For example, ethylenebis(triphenylphosphine)platinum(0), [(C6H5)3P]2Pt(H2C=CH2), wherein the platinum is three-coordinate and zero-valent (Zeise's salt is a derivative of platinum(II)).

References

  1. ^ Aldrich datasheet
  2. ^ Chock, P. B.; Halpern, J.; Paulik, F. E.; Shupack, Saul I.; Deangelis, Thomas P. (1990). Potassium Trichloro(Ethene)Platinate(II) (Zeise's Salt). 28. pp. 349–351. doi:10.1002/9780470132593.ch90. 
  3. ^ Elschenbroich, C. ”Organometallics : A Concise Introduction” (2006) Wiley-VCH: Weinheim. ISBN 978-3-527-29390-2
  4. ^ Zeise, W. C. (1831). "Von der Wirkung zwischen Platinchlorid und Alkohol, und von den dabei entstehenden neuen Substanzen". Annalen der Physik und Chemie 97 (4): 497. doi:10.1002/andp.18310970402. 
  5. ^ R. A. Love, T. F. Koetzle, G. J. B. Williams, L. C. Andrews, R. Bau (1975). "Neutron diffraction study of the structure of Zeise's salt, KPtCl3•C2H4•H2O". Inorganic Chemistry 14 (11): 2653–2657. doi:10.1021/ic50153a012. 
  6. ^ L. B. Hunt (1984). "The First Organometallic Compounds: WILLIAM CHRISTOPHER ZEISE AND HIS PLATINUM COMPLEXES". Platinum Metals Review 28 (2): 76–83. http://www.platinummetalsreview.com/pdf/pmr-v28-i2-076-083.pdf. 
  7. ^ M. Black, R. H. B. Mais and P. G. Owston (1969). "The crystal and molecular structure of Zeise's salt, KPtCl3•C2H4•H2O". Acta Crystallographica Section B B25 (9): 1753–1759. doi:10.1107/S0567740869004699.