Potassium diplatinum(II) tetrakispyrophosphite explained

Potassium diplatinum(II) tetrakispyrophosphite (abbreviated as [Pt<sub>2</sub>(pop)<sub>4</sub>]4−) is the inorganic compound with the formula K4[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 nm and a lifetime near 10 μs.[1]

Synthesis and reactions

The complex is prepared by heating a mixture of potassium tetrachloroplatinate and phosphorous acid:[2]

2K2PtCl4 + 8H3PO3 → K4[Pt<sub>2</sub>(HO<sub>2</sub>POPO<sub>2</sub>H)<sub>4</sub>] + 8HCl + 4H2OSeveral quat salt derivatives are known.[3] [4]

The anion reacts with boron trifluoride to give the BF2-capped complex [Pt<sub>2</sub>(P<sub>2</sub>PO<sub>5</sub>)<sub>4</sub>(BF<sub>2</sub>)<sub>8</sub>]4-.[5]

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

K4[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 pair of square-planar platinum(II) centers are bridged by four pyrophosphito (HO(O)POP(O)OH2-) 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.[1]

References

  1. 10.1021/ar00158a002. Pyrophosphito-Bridged Diplatinum Chemistry. 1989. Roundhill. D. Max. Gray. Harry B.. Che. Chi Ming. Accounts of Chemical Research. 22. 2. 55–61.
  2. 10.1002/9780470132555.ch61. Potassium Tetrakis[Dihydrogen Diphosphito(2-)]Diplatinate(II). Inorganic Syntheses. 1986. Alexander. K. A.. Bryan. S. A.. Dickson. M. K.. Hedden. D.. Roundhill. D. Max. 211–213.
  3. 10.1246/bcsj.77.933. X-ray Analysis of Excited-State Structures of the Diplatinum Complex Anions in Five Crystals with Different Cations. 2004. Yasuda. Nobuhiro. Uekusa. Hidehiro. Ohashi. Yuji. Bulletin of the Chemical Society of Japan. 77. 5. 933–944.
  4. 10.1021/ic301469u. Controlling the Electronic States and Physical Properties of MMX-Type Diplatinum-Iodide Chain Complexes via Binary Countercations. 2012. Iguchi. Hiroaki. Takaishi. Shinya. Breedlove. Brian K.. Yamashita. Masahiro. Matsuzaki. Hiroyuki. Okamoto. Hiroshi. Inorganic Chemistry. 51. 18. 9967–9977. 22946488.
  5. 10.1021/acs.inorgchem.5b00063. Spin–Orbit TDDFT Electronic Structure of Diplatinum(II,II) Complexes. 2015. Záliš. Stanislav. Lam. Yan-Choi. Gray. Harry B.. Vlček. Antonín. Inorganic Chemistry. 54. 7. 3491–3500. 25775368. free.