- Synthesis and reactivity of diphosphino Pt(II) silanolate complexes as molecular models of the interaction of platinum particles with silica
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A series of di- and monosubstituted cis-platinum(II) silanolate complexes, Pt(OSiR3)2(dppe) (R=Et, 1; R=Me, 2) and Pt(OSiR3)Cl(dppe) (R=Et, 3; R=iPr, 4) where dppe is 1,2-bis(diphenylphosphino)ethane, have been isolated and characterised spectroscopically. Complex 1 does not react with CO and H2 under anhydrous conditions, but the complexes Pt{C(O)OCH3)}2(dppe) (6) and Pt(CO3)(dppe) (7) have been isolated bubbling CO in methanol and CO2 in moist benzene solutions of 1, respectively. The behaviour of 1 towards water or methanol is discussed on the basis of 1H, and 31P{1H} NMR spectroscopic data. The new complex Pt{S2C(OSiEt3)2}(dppe) (8) has been isolated by reaction of 1 with CS2 in benzene solution. This reactivity would suggest a high sensitivity towards water, but not towards H2 or CO, of the bonding of slightly oxidised platinum particles with silanol groups of silica surface. 2002 Elsevier Science B.V. All rights reserved.
- Banditelli, Guido,Pizzotti, Maddalena,Bandini, Anna Laura,Zucchi, Claudia
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- Syntheses, Spectra, and Structures of (Diphosphine)platinum(II) Carbonate Complexes
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A variety of (diphosphine)platinum(II) carbonate complexes, (LL)Pt(CO3), are readily prepared from the corresponding (diphosphine)platinum dichlorides by treatment with silver carbonate in dichoromethane solution provided that water is present. This reaction also permits facile preparation of analogous 13C-labeled complexes. The carbonate ligands in these complexes have been characterized by IR and 13C NMR spectroscopy. Alternative preparative routes involve conversion of the precursor dichlorides to the corresponding dialkoxides or diphenoxides, followed by treatment with water and carbon dioxide. Various reaction intermediates have been spectroscopically observed in the latter syntheses. Two crystalline modifications of (Ph2PCH2CH2CH2PPh 2)Pt(CO3), one with and one without a dichloromethane of solvation, have been studied by single-crystal X-ray diffraction. Crystal data for PtP2O3C28H26: P21/c, Z = 4, T = 200 K, a = 10.362(8) ?, b = 14.743(6) ?, c = 19.183(10) ?, β = 122.69(6)°. Crystal data for PtP2O3C28H26·CH 2Cl2: P21/c, Z = 4, T ≈ 298 K, a = 11.744(2) ?, b = 15.526(3) ?, c = 15.866(3) ?, β = 101.58(1)°.
- Andrews, Mark A.,Gould, George L.,Klooster, Wim T.,Koenig, Kristina S.,Voss, Eric J.
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p. 5478 - 5483
(2008/10/09)
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- Photochemical reactions of diphosphineplatinum(II) oxalate complexes
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Irradiation at 254 nm of CH3CN/C6H6 or PhCn solutions of produces 2 equiv. of CO2, and in the presence of PhCl or PhI yields .With CO or PhCCPh the products are or CPh)(dppe)>, but in the latter case extended photolysis yields CPh)(dppe)>.Photolysis in the presence of H2 gives a mixture of the + and + cations.Simple elimination of CO2 does not occur in all cases, as illustrated by the formation of when is photolyzed in the presence of methanol.Photochemical reactions of the related complexes (L2 = dppm, dcpe) are also described.
- Anderson, Gordon K.,Lumetta, Gregg J.,Siria, Jeffrey W.
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p. 253 - 259
(2007/10/02)
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