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Potassium diplatinum(II) tetrakispyrophosphite

Potassium diplatinum(II) tetrakispyrophosphite (abbreviated as [Pt<sub>2</sub>(pop)<sub>4</sub>]<sup>4−</sup>) is the inorganic compound with the formula K<sub>4</sub>[Pt<sub>2</sub>(HO<sub>2</sub>POPO<sub>2</sub>H)<sub>4</sub>]. It is a water-soluble yellow salt. The compound has a long-lived, strongly luminescent excited state, with an emission maximum at ~510&nbsp;nm and a lifetime near 10&nbsp;μs.

Synthesis and reactions

The complex is prepared by heating a mixture of potassium tetrachloroplatinate and phosphorous acid:

2K<sub>2</sub>PtCl<sub>4</sub> + 8H<sub>3</sub>PO<sub>3</sub> → K<sub>4</sub>[Pt<sub>2</sub>(HO<sub>2</sub>POPO<sub>2</sub>H)<sub>4</sub>] + 8HCl + 4H<sub>2</sub>O

Several quat salt derivatives are known.

The anion reacts with boron trifluoride to give the BF<sub>2</sub>-capped complex [Pt<sub>2</sub>(P<sub>2</sub>PO<sub>5</sub>)<sub>4</sub>(BF<sub>2</sub>)<sub>8</sub>]<sup>4-</sup>.

The compound reacts with halogens to give Pt(III) dimers:

K<sub>4</sub>[Pt<sub>2</sub>(HO<sub>2</sub>POPO<sub>2</sub>H)<sub>4</sub> + Cl<sub>2</sub> → K<sub>4</sub>[Pt<sub>2</sub>(HO<sub>2</sub>POPO<sub>2</sub>H)<sub>4</sub>Cl<sub>2</sub>]

With substoichiometric halogen, linear chain compounds result.

Structure

The anion is an example of the Chinese lantern structure. The two square-planar platinum(II) centers are bridged by four pyrophosphito (HO(O)POP(O)OH<sup>2-</sup>) ligands. The ligands interact via hydrogen bonds between the POH and P=O group. The Pt---Pt separation is 293 pm for the dihydrate. In the Pt(III) dichloride, the Pt-Pt distance is 270 pm, indicating Pt-Pt bonding.

References