Potassium diplatinum(II) tetrakispyrophosphite
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| Names | |
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| Other names
platinum pop
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| Identifiers | |
3D model (JSmol)
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| Properties | |
| H8K4O20P8Pt2 | |
| Molar mass | 1122.395 g·mol−1 |
| Appearance | yellow solid |
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
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Potassium diplatinum(II) tetrakispyrophosphite (abbreviated as [Pt2(pop)4]4−) is the inorganic compound with the formula K4[Pt2(HO2POPO2H)4]. 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
[edit]The complex is prepared by heating a mixture of potassium tetrachloroplatinate and phosphorous acid:[2]
- 2 K2PtCl4 + 8 H3PO3 → K4[Pt2(HO2POPO2H)4] + 8 HCl + 4 H2O
Several quat salt derivatives are known.[3][4]
The anion reacts with boron trifluoride to give the BF2-capped complex [Pt2(P2PO5)4(BF2)8]4-.[5]
The compound reacts with halogens to give Pt(III) dimers:
- K4[Pt2(HO2POPO2H)4 + Cl2 → K4[Pt2(HO2POPO2H)4Cl2]
With substoichiometric halogen, linear chain compounds result.
Structure
[edit]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
[edit]- ^ a b Roundhill, D. Max; Gray, Harry B.; Che, Chi Ming (1989). "Pyrophosphito-Bridged Diplatinum Chemistry". Accounts of Chemical Research. 22 (2): 55–61. doi:10.1021/ar00158a002.
- ^ Alexander, K. A.; Bryan, S. A.; Dickson, M. K.; Hedden, D.; Roundhill, D. Max (1986). "Potassium Tetrakis[Dihydrogen Diphosphito(2-)]Diplatinate(II)". Inorganic Syntheses: 211–213. doi:10.1002/9780470132555.ch61.
- ^ Yasuda, Nobuhiro; Uekusa, Hidehiro; Ohashi, Yuji (2004). "X-ray Analysis of Excited-State Structures of the Diplatinum Complex Anions in Five Crystals with Different Cations". Bulletin of the Chemical Society of Japan. 77 (5): 933–944. doi:10.1246/bcsj.77.933.
- ^ Iguchi, Hiroaki; Takaishi, Shinya; Breedlove, Brian K.; Yamashita, Masahiro; Matsuzaki, Hiroyuki; Okamoto, Hiroshi (2012). "Controlling the Electronic States and Physical Properties of MMX-Type Diplatinum-Iodide Chain Complexes via Binary Countercations". Inorganic Chemistry. 51 (18): 9967–9977. doi:10.1021/ic301469u. PMID 22946488.
- ^ Záliš, Stanislav; Lam, Yan-Choi; Gray, Harry B.; Vlček, Antonín (2015). "Spin–Orbit TDDFT Electronic Structure of Diplatinum(II,II) Complexes". Inorganic Chemistry. 54 (7): 3491–3500. doi:10.1021/acs.inorgchem.5b00063. PMID 25775368.