Palladium(II) cyanide

Palladium(II) cyanide

Names
IUPAC name Palladium(2+) dicyanide
Identifiers
CAS Number	2035-66-7
ChemSpider	67420
Jmol 3D model	Interactive image
PubChem	6093464
InChI InChI=1S/2CN.Pd/c2*1-2;/q2*-1;+2 Key: XDASSWBZWFFNPX-UHFFFAOYSA-N InChI=1/2CN.Pd/c2*1-2;/q2*-1;+2 Key: XDASSWBZWFFNPX-UHFFFAOYAK
SMILES [Pd+2].[C-]#N.[C-]#N
Properties
Chemical formula	Pd(CN)2
Molar mass	158.455 g/mol
Vapor pressure	{{{value}}}
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
Infobox references

Palladium(II) cyanides are chemical species with the empirical formula Pd(CN)_n^(2-n)−. The dicyanide (n = 2, CAS: [2035-66-7]) is a coordination polymer which was the first pure palladium compound isolated. In his attempts to produce pure platinum metal in 1804, W.H. Wollaston added mercuric cyanide to a solution of impure platinum metal in aqua regia to precipitate palladium cyanide which was then ignited to recover palladium metal - a new element. It had long been suspected that the structure of palladium cyanide consists of square planar Pd(II) centers linked by bridging cyanide ligands, which are bonded through both the carbon and nitrogen atoms. The CN stretch in the infrared spectra of Pd(CN)₂, at 2222 cm⁻¹, is typical of bridging cyanide ions. It is now known that the compound commonly known as "Palladium(II) cyanide" is in fact a nanocrystaline material better described using the formula Pd(CN)₂^.0.29H₂O. The interior of the sheets do indeed consist of square-planar palladium ions linked by head-to-tail disordered bridging cyanide groups to form 4,4-nets. These sheets are approximately 3 nm x 3 nm in size and are terminated by an equal number of water and cyanide groups maintaining the charge neutrality of the sheets. These sheets then stack with very little long range order resulting in Bragg diffraction patterns with very broad peaks. The Pd-C and Pd-N bond lengths, determined using total neutron diffraction, are both 1.98 Å.

The compound is rather insoluble in water with a solubility product of log K_sp = -42.

The slightly more topical palladium(II) cyanide is the dianion [Pd(CN)₄]²⁻. The equilibrium constant for the competition reaction

PdL²⁺ + 4CN⁻ ⇌ [Pd(CN)₄]²⁻ + L, L = 1,4,8,11-tetraazaundecane (2,3,2-tet)

was found to have a value of log K = 14.5. Combination with the formation of the palladium complex with the tetradentate ligand

[Pd(H₂O)₄]²⁺ + L ⇌ PdL²⁺ + 4 H₂O, log K = 47.9

gives

[Pd(H₂O)₄]²⁺ + 4CN⁻ ⇌ [Pd(CN)₄]²⁻ + 4H₂O, log β₄ = 62.3.

This appears to be the highest formation constant known for any metal ion.

The affinity of Pd for cyanide is so great that palladium metal is attacked by cyanide solutions:

Pd(s) + 2 H⁺ + 4 CN⁻ ⇌ [Pd(CN)₄]²⁻ + H₂

This reaction is reminiscent of the “cyanide process” for the extraction of gold, although in the latter reaction O₂ is proposed to be involved, to give H₂O.

Exchange of between free cyanide ion and [Pd(CN)₄]²⁻ has been evaluated by ¹³C NMR spectroscopy. That exchange occurs at all illustrates the ability of some compounds to be labile (fast reactions) but also stable (high formation constants). The reaction rate is described as follows:

rate = k₂[M(CN)₄²⁻][CN⁻], where k₂ 120 M⁻¹⁻s⁻¹

The bimolecular kinetics implicate a so-called associative pathway. The associative mechanism of exchange entails rate-limiting attack of cyanide on [Pd(CN)₄]²⁻, possibly with the intermediacy of a highly reactive pentacoordinate species [Pd(CN)₅]³⁻. By comparison, the rate constant for [Ni(CN)₄]²⁻ is > 500,000 M⁻¹⁻s⁻¹, whereas [Pt(CN)₄]²⁻exchanges more slowly at 26 M⁻¹s⁻¹. Such associative reactions are characterized by large negative entropies of activation, in this case: -178 and -143 kJ/(mol·K) for Pd and Pt, respectively.

In organic synthesis palladium cyanide is used in the synthesis of olefinic cyanides from olefins. and as a catalyst in the regioselective reaction between cyanotrimethylsilane and oxiranes .