Krogmann's salt

Krogmann's salt

Names
IUPAC name Dipotassium tetracyanoplatinate bromide trihydrate
Other names Potassium tetracyanoplatinate bromide trihydrate
Properties
Chemical formula	K2Pt(CN)4Br0.3
Molar mass	401.3227 g/mol
Appearance	Copper-colored crystalline solid
Structure
Crystal structure	Tetragonal
Coordination geometry	Square planar
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
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Infobox references

Krogmann's salt is a mixed-valence square planar coordination complex of platinum and cyanide bonded through linear platinum metal chains, sometimes described as molecular wires.

Although the term Krogmann’s salt most commonly refers to a platinum metal complex of the formula K₂[Pt(CN)₄X_0.3] where X is usually bromine (or sometimes chlorine), a number of non-stoichiometric metal salts containing the anionic complex [Pt(CN)₄]²⁻ can also be characterized under the blanket term “Krogmann’s salts.”

Modeled as an infinite one-dimensional molecular chain of platinum atoms, the high anisotropy and restricted dimensionality of Krogmann’s salt and related compounds are becoming increasingly attractive properties for many facets of nanotechnology.^[1]

History

Krogmann’s salt was first synthesized by Dr. Klaus Krogmann in the late 1960s at the University of Stuttgart in Germany. Dr. Krogmann published the original journal article documenting the synthesis and characterization of the salt in 1969.^[2]

Structure and physical properties

n[Pt(CN)₄]²⁻ → ([Pt(CN)₄]^1.7−)_n

Krogmann’s salt is a series of partially oxidized tetracyanoplatinate complexes linked by the platinum-platinum bonds on the top and bottom faces of the planar [Pt(CN)₄]ⁿ⁻ anions. This salt forms infinite stacks in the solid state based on the overlap of the d_z2 orbitals.^[1]

Krogmann’s salt has a tetragonal crystal structure with a Pt-Pt distance of 2.880 angstroms, which is much shorter than the metal-metal bond distances in other planar platinum complexes such as Ca[Pt(CN)₄]·5H₂O (3.36 angstroms), Sr[Pt(CN)₄]·5H₂O (3.58 angstroms), and Mg[Pt(CN)₄]·7H₂O (3.16 angstroms).^[2][3] The Pt-Pt distance in Krogmann's salt is only 0.1 angstroms longer than in platinum metal.^[4]

Each unit cell contains a site for Cl⁻, corresponding to 0.5 Cl⁻ per Pt. However, this site is only filled 64% of the time, giving 0.32 Cl⁻ per Pt in the actual compound. Because of this, the oxidation number of Pt does not rise above +2.32.^[2]

Krogmann’s salt has no recognizable phase range and is characterized by broad and intense intervalence bands in its electronic spectra.^[5]

Chemical properties

One of the most widely researched properties of Krogmann’s salt is its unusual electric conductance. Because of its linear chain structure and overlap of the platinum $d_{{z^{2}}}$ orbitals, Krogmann’s salt is an excellent conductor of electricity.^[1] This property makes it an attractive material for nanotechnology.^[6]

Preparation

The usual preparation of Krogmann's salt involves the evaporation of a 5:1 molar ratio mixture of the salts K₂[Pt(CN)₄] and K₂[Pt(CN)₄Br₂] in water to give copper-colored needles of K₂[Pt(CN)₄]Br_0.32·2.6 H₂O.

5K₂[Pt(CN)₄] + K₂[Pt(CN)₄Br₂] + 15.6 H₂O → 6K₂[Pt(CN)₄]Br_0.32·2.6 H₂O

Because excess Pt^II or Pt^IV complex crystallizes out with the product when the reactant ratio is changed, the product is therefore well defined, although non-stoichiometric.^[2]

Uses

Although there was a large body of research and literature generated on molecular wire-type metal complexes through the mid-1980s, interest in stacked metal-metal bonds saw a decline until only very recently.

Due to the explosion of nanotechnology in the last few years, many researchers have taken a renewed interest in Krogmann’s salt and its related compounds due to their high anisotropy, restricted dimensionality, and unique conductance properties.

A new group of platinum chains based on alternating cations and anions of [Pt(CNR)₄]²⁺ (R = iPr, c-C₁₂H₂₃, p-(C₂H₅)C₆H₄) and [Pt(CN)₄]²⁻ is undergoing current research.^[1] These may be able to be used as vapochromic sensor materials, or materials which change color when exposed to different vapors.^[7][8][9]

Similar to Krogmann’s platinum salt, it has been shown that it is possible to stabilize metal chains with only unsaturated hydrocarbons, or olefins. Current research indicates that mononuclear Pd⁰ and Pd^II react with conjugated polyenes to give linear chains of Pd-Pd bonds protected by a “π-electron sheath.”^[1][10]

Not only do these olefin-stabilized metal chains constitute a significant contribution to the field of organometallic chemistry, both the complex’s metal atom structures and the olefin ligands themselves can conduct a current.^[1][11] The prospect of creating molecular wires of conducting organic and inorganic constituents has intriguing possibilities for future research, especially in microbiology, nanotechnology, and organic circuitry.

References

1. Bera, J. K.; Dunbar, K. R. (2002). "Chain Compounds Based on Transition Metal Backbones: New Life for an Old Topic". Angew. Chem. Int. Ed. 41 (23): 4453–4457. doi:10.1002/1521-3773(20021202)41:23<4453::AID-ANIE4453>3.0.CO;2-1. PMID 12458505.
2. Krogmann, K. (1969). "Planare Komplexe mit Metall-Metall-Bindungen". Angew. Chem. (in German). 81 (1): 10–17. doi:10.1002/ange.19690810103. Krogmann, K. (1969). "Planar Complexes Containing Metal-Metal Bonds". Angew. Chem. Int. Ed. Engl. 8 (1): 35–42. doi:10.1002/anie.196900351.
3. Krogmann, K.; Hausen, H. D. Z. (1968). "Pt-Chain Structures. 1. Potassium Tetracyanoplatinate Violets K₂[Pt(CN)₄]X_0,3·2,5H₂O (X=Cl,Br)". Z. Anorg. Allg. Chem. 358: 67.
4. Heger, G.; Deiseroth, H.J.; Schulz, H. "Combined X-ray and neutron diffraction study of K2 (Pt(CN)₄)X_0.3^.3(H₂O) with X= Br, Cl (KCP) between 31 K and room temperature" Acta Crystallographica B 1982, volume 24,1968-38. (1978) 34, p725-p731.
5. Clar, R. J. H.; Cround, V. B.; Khokhar, A. R. (1987). "Neutral chain chloride- and bromide-bridged platinum(II,IV) complexes of 1,2-diaminocyclohexane: synthesis and electronic, infrared, Raman, and resonance Raman studies". Inorg. Chem. 26 (20): 3284–3290. doi:10.1021/ic00267a014.
6. Wu, D. Y.; Zhang, T. L. (2004). "Recent developments in linear chain clusters of low-valent platinum group metals". Prog. Chem. (in Chinese). 16 (6): 911–917.
7. Grate, J. W.; Moore, L. K.; Janzen, D. E.; Veltkamp, D. J.; Kaganove, S.; Drew, S. M.; Mann, K. R. (2002). "Steplike Response Behavior of a New Vapochromic Platinum Complex Observed with Simultaneous Acoustic Wave Sensor and Optical Reflectance Measurements". Chem. Matter. 14 (3): 1058–1066. doi:10.1021/cm0104506.
8. Buss, C.E.; Mann, K.R. (2002). "Synthesis and Characterization of Pt(CN-p-(C₂H₅)C₆H₄)₂(CN)₂, a Crystalline Vapoluminescent Compound That Detects Vapor-Phase Aromatic Hydrocarbons". J. Am. Chem. Soc. 124 (6): 1031–1039. doi:10.1021/ja011986v.
9. Buss, C.E.; Anderson, C.E.; Pomije, M. K.; Lutz, C. M.; Britton, D.; Mann, K. R. (1998). "Structural Investigations of Vapochromic Behavior. X-ray Single-Crystal and Powder Diffraction Studies of [Pt(CN-iso-C₃H₇)₄][M(CN)₄] for M = Pt or Pd". J. Am. Chem. Soc. 120 (31): 7783–7790. doi:10.1021/ja981218c.
10. T., Mino, Y., Mochizuki, E., Kai, Y., Kurosawa, H. (2001). "Reversible Interconversion between Dinuclear Sandwich and Half-Sandwich Complexes: Unique Dynamic Behavior of a Pd-Pd Moiety Surrounded by an sp²-Carbon Framework". J. Am. Chem. Soc. 123 (28): 6927–6928. doi:10.1021/ja010027y.
11. Murahashi, T.,Nagai, Okuno, T., Matsutani, T., Kurosawa, H. (2000). "Synthesis and ligand substitution reactions of a homoleptic acetonitrile dipalladium(I) complex". Chem. Commun. (17): 1689–1690. doi:10.1039/b004726k.