Tetracyanoplatinates

Spectroscopic properties of the quasi-one-dimensional tetracyanoplatinate(II) compounds. G. Glie-mann and H. Yersin, Struct. Bonding (Berlin), 1985, 62, 88 (181). 

Gleitzer C, Goodenough JB (1985) Mixed-Valance Iron Oxides. 61 1-76 Gliemann G, Yersin H (1985) Spectroscopic Properties of the Quasi One-Dimensional Tetracyanoplatinate(II) Compounds. 62 87-153 Golovina AP, Zorov NB, Runov VK (1981) Chemical Luminescence Analysis of Inorganic substances. 47 53-119... 

In the early stage of the development of molecular conductors based on metal complexes, partially oxidized tetracyanoplatinate salts (for example, KCP K2 [Pt(CN)4]Br0.30-3H2O) and related materials were intensively studied [6], In this system, the square-planar platinum complexes are stacked to form a linear Pt-atom chain. The conduction band originates from the overlap of 5dz2 orbitals of the central platinum atom and exhibits the one-dimensional character. 

A. CESIUM TETRACYANOPLATINATE (2 1) MONOHYDRATE AND CESIUM TETRACYANOPLATINATE (1.75 1) DIHYDRATE... 

Dipotassium tetracyanoplatinate(II) trihydrate (4.0 g, 9.3 X 10"3 mole) is dissolved in 8 mL of hot water (70°) in a polypropylene beaker and acidified with 1 M H2S047 (pH 1-2). Only 0.5 mL(3.1 X 10 3 mole) of 20% H202 is required for oxidation. The rest of the procedure is identical to that in Section A for cesium tetracyanoplatinate (1.75 1) dihydrate, with the exception that after cooling for about 24 hours, and prior to collection of the crystals, the beaker is placed in a desiccator under reduced pressure over magnesium perchlorate and allowed to stand until about 5 mL of solution remains. 

Partially oxidized tetracyanoplatinates have attracted much attention in recent years because of their highly anisotropic physical properties.1 Although partially oxidized salts of K+, Na+, Rb and Mg+2 have been reported, the analogous bromide-deficient guanidinium salt is the only such compound containing an organic cation.2 A procedure for the preparation of this guanidinium salt has not been previously reported. 

Potassium tetracyanoplatinate may be prepared as described elsewhere in this volume,3 or commercial material may be used after chloride impurities are eliminated by two recrystallizations from distilled water. An aqueous solution at... 

In addition to the partially oxidized tetracyanoplatinates, bis(oxalato)platinate-(II) can be nonstoichiometrically oxidized by chemical oxidants13 to form highly lustrous needlelike crystals containing platinum in the 2.36 oxidation state. These complexes have not been characterized to the extent of the tetracyano-platinate complexes however, the oxalato complexes are reported to be highly conducting.13 The starting material is bis(oxalato)platinate(II), which can be prepared in 30% yields from hexachloroplatinate(lV) and potassium oxalate.9... 

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