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• W2005282180 abstract "The five-membered metallacycle Cp2Zr(CR1=CR2CR2=CR1) (1, R1 = SiMe3, R2 = Ph) is a suitable starting material for the in situ generation of the reactive (η2-phenyltrimethylsilylethyne)zirconocene (3). Thus, thermolysis of 1 (70°C) with trimethylphosphane gives Cp2Zr(Me3SiC*z.tbnd;CPh)(PMe3) (8) and free Me3SiCCPh (4). Subsequent reaction of 8 with acetophenone produces Cp2Zr[CR1=CR2CMePhO] (9, R1 = SiMe3, R2 = Ph). Thermolysis of 1 in the presence of CpW(CO)3H also results in the liberation of one quivalent of 4. The reactive intermediate 3 is protonated to give Cp2Zr(CR1=CHR2)(μ-OC)W(CO)2CP (12, R1 = SiMe3, R2 = Ph). Treatment of 1 with [HNEt3][BPh4] in acetonitrile gives the cationic Cp2Zr(CR1=CR2CMe=NH)(CH3CN)+ (3a: R1 = SiMe3, R2 = Ph) and its regioisomer 13b (R1 and R2 exchanged). There is evidence that the complexes 13 are formed by acetonitrile addition to thermally-generated 3 to give Cp2Zr(CR1=CR2CMe=N), which is then subsequently protonated at the basic ring nitrogen. These reactions show that a readily available metallacyclopentadiene system can be used as a convenient synthetic equivalent of a very reactive (η2-alkyne)metallocene complex by thermally induced equilibration in the presence of suitable trapping reagents." @default.
• W2005282180 created "2016-06-24" @default.
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• W2005282180 date "1991-05-01" @default.
• W2005282180 modified "2023-10-17" @default.
• W2005282180 title "Reactionsof in situ generated (η2-phenyltrimethylsilylacetylene)zirconocene" @default.
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• W2005282180 doi "https://doi.org/10.1016/0022-328x(91)86143-e" @default.
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