Synthesis and Reactivity of Cyclotriphosphazenes Bearing Reactive SilaneFunctionalities: Novel Derivatives via Hydrosilylation Reactions

摘要

Cyclotriphosphazenes with the general structure N3P3(OPh),5NH(CH2)3SiMe2OEt reactwith lithium aluminum hydride in diethyl ether to produce N3P3(OPh).5NH(CH2)3SiMe2H. Subsequent reaction of this species with alkenes in the presence of a platinum catalyst produced new cyclotriphosphazenes bearing alkoxy, siloxy, glycidyl, and ferrocenyl side groups. The yields depended on the type of catalyst and olefin used. Tetramethyl-1,3-divinyldisiloxane-platinum complex (DVDS:Pt) was a more efficient hydrosilylation catalyst than hydrogen hexachloroplatinic acid (CPA). Use of the latter catalyst yielded the silanol N3P3(OPh)5NH(CH2)3SiMe2OH, as a side product. This derivative subsequently condensed to produce a ring-linked phosphazene species. The hydrosilylation products were studied by 31p, 1H, and 13C NMR and infrared spectroscopy, elemental analysis, and mass spectrometry. Analogous reactions were investigated with the high-polymeric counterparts. Polymers with the general structure NPR1.8(NH(CH2)3SiMe2OEt)0.2)n, where R is -OCH2CF3 or -OC,H5, were synthesized and allowed to react with LiAlH,. The reduction process induced significant molecular weight decline from phosphorus-nitrogen bond cleavage, which was probably initiated by coordination of the aluminum to the nitrogen atoms in the polymer backbone and the amino side group. The influence of complexing agents, such as 4-(dimethylamino)pyridine (DMAP) and Et3N, on the reduction reactions was investigated. Organometallic, Phosphazenes, Synthesis.