- Fluoridative degradation of cyclosiloxanes with alkali metal salts of perfluorinated complex anion. Part 5
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Alkali metal salts of perfluorinated 'non-nucleophilic' complex anions were used for fluoridative degradation of cyclosiloxanes under thermal conditions in the absence and presence of high boiling multifunctional etheral solvent. The degradative products
- Farooq, Omar
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- Cyclic Platina(borasiloxane)s and Platina(siloxane)s and Their Chemical Properties
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[Pt(SiHPh2)2(dmpe)] (dmpe = 1,2-bis(dimethylphosphino)ethane) reacts with arylboronic acids to produce six-membered platinacycles [Pt(SiPh2-O-BAr-O-SiPh2)(dmpe)] (Ar = C6H4-4-COMe (1a), C6H4-4-CF3 (1b)). X-ray crystallography of 1a revealed the structure having a planar six-membered ring, composed of Pt, O, B, and Si atoms. Reaction of H2O with [Pt(SiHPh2)2(dmpe)] formed a four-membered cyclic complex, [Pt(SiPh2-O-SiPh2)(dmpe)] (2), which was observed in the initial reaction mixture of 4-acetylphenylboronic acid with [Pt(SiHPh2)2(dmpe)]. Exposure of solutions of [Pt(SiHPh2)2(dmpe)] and of [Pt(SiHAr2)2(PMe3)2] (Ar = Ph, C6H4-4-Me) to air resulted in the formation of the cyclic platina(siloxane)s, [Pt(O-SiPh2-O-SiPh2-O)(dmpe)] (3) and [Pt(O-SiAr2-O-SiAr2-O)(PMe3)2] (4: Ar = Ph; 5: Ar = C6H4-4-Me), respectively. The six-membered platina(borasiloxane) 1a reacts with H2GePh2 and with CF3CO2H to release the cyclic borasiloxanes as the products. The former reaction affords [Pt(GeHPh2)2(dmpe)], while the latter produces [Pt(OCOCF3)2(dmpe)] as the Pt-containing products. A similar reaction of HCl with platina(siloxane) 4 gives a disiloxanediol via cleavage of the Pt-O bonds. Complex 4 reacts with H2SiPh2 to form a triplatinum complex, [{Pt(PMe3)}3(μ-SiPh2)3] (15), which is obtained under milder conditions than the previously reported reaction starting from [Pt(SiHPh2)2(PMe3)2].
- Noda, Hiroki,Tanaka, Kimiya,Tanabe, Makoto,Osakada, Kohtaro
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