Neutral and anionic binuclear perhalogenophenyl platinum–silver complexes with Pt→Ag bonds unsupported by covalent bridges. Molecular structures of [(tht)(C6Cl5)(C6F5)2-PtAg(PPh3)], [NBu4][(C6F5)4PtAg(tht)] and [NBu4][cis-(C6Cl5)2(C6F5)2PtAg(tht)](tht = tetrahydrothiophene)
- 1 January 1991
- journal article
- research article
- Published by Royal Society of Chemistry (RSC) in J. Chem. Soc., Dalton Trans.
- No. 9,p. 2253-2264
- https://doi.org/10.1039/dt9910002253
Abstract
Heterobinuclear complexes of general formula [L(C6Cl5)3-x(C6F5)xPtAg(PPh3)][x= 2–0; L = tht (tetrahydrothiophene), PPh3 or pyridine (py)]14–21 have been prepared by treating the anionic platinum derivatives [NBu4][PtL(C6F5)x(C6Cl5)3-x] with [Ag(OCIO3)(PPh3)](molar ratio 1 : 1) in dichloromethane. The anionic [NBu4][(C6F5)4PtAgL](L = OEt2, PPh3 or tht)22–24 and [NBu4][cis-(C6Cl5)2(C6F5)2PtAg(tht)]25 have been obtained from the corresponding [NBu4]2[Pt(C6X5)2(C6X′5)2] and [Ag(OCIO3)L](molar ratio 1 : 1) in CH2Cl2–diethyl ether. The reaction between [NBu4][Pd(C6F5)3(tht)] and [Ag(OCIO3)(PPh3)] renders Ag(C6F5) and cis-[Pd(C6F5)2(PPh3)(tht)]. The salts [NBu4]2[Pt(C6Cl5)4] and [NBu4]2[Pd(C6F5)4] react with [Ag(OCIO3)(tht)] yielding [NBu4][Pt(C6Cl5)3(tht)] and [NBu4][Pd(C6F5)3(tht)], respectively. The reactions between [NBu4]2[Pt(C6F5)4] and [Ag(OCIO3)(tht)] or [Ag(OCIO3)(PPh3)](molar ratio 1:2) render in the first case complex 24 while in the second an unstable material which evolves to [(Ph3P)(C6F5)3PtAg(PPh3)]27 is obtained. The reaction between [NBu4]2[trans-PtCl2(C6X5)2](X = F or Cl) and [Ag(OCIO3)(tht)] or [Ag(tht)2]ClO4 have also been studied. The structures of [(tht)(C6Cl5)(C6F5)2PtAg(PPh3)]14, [NBu4][(C6F5)4PtAg(tht)]24 and [NBu4][cis-(C6Cl5)2PtAg(tht)]25 have been established by single-crystal X-ray diffraction studies. The complexes contain a strong Pt→Ag bond [2.650(2), 14; 2.641(1), 24; and 2.692(2)Å, 25] unsupported by covalent bridges, and short contacts between the o-F or o-Cl atoms of the C6X5(X = F or Cl) groups and the Ag atom are present. The relative strength of such contacts is discussed. Methods for the synthesis of mixed pentachloro-pentafluoro-phenyl starting complexes 1–13 have been investigated.Keywords
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