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- W1972070055 abstract "Abstract Reactions of Group 4 metallocene alkyne complexes [Cp′ 2 M(η 2 ‐Me 3 SiC 2 SiMe 3 )] ( 1 : M=Zr, Cp′=Cp*=η 5 ‐pentamethylcyclopentadienyl; 2 a : M=Ti, Cp′=Cp*, and 2 b : M=Ti, Cp′ 2 = rac ‐(ebthi)= rac ‐1,2‐ethylene‐1,1′‐bis(η 5 ‐tetrahydroindenyl)) with diphenylacetonitrile (Ph 2 CHCN) and of the seven‐membered zirconacyclocumulene 3 with phenylacetonitrile (PhCH 2 CN) were investigated. Different compounds were obtained depending on the metal, the cyclopentadienyl ligand and the reaction temperature. In the first step, Ph 2 CHCN coordinated to 1 to form [Cp* 2 Zr(η 2 ‐Me 3 SiC 2 SiMe 3 )(NCCHPh 2 )] ( 4 ). Higher temperatures led to elimination of the alkyne, coordination of a second Ph 2 CHCN and transformation of the nitriles to a keteniminate and an imine ligand in [Cp* 2 Zr(NC 2 Ph 2 )(NCHCHPh 2 )] ( 5 ). The conversion of 4 to 5 was monitored by using 1 H NMR spectroscopy. The analogue titanocene complex 2 a eliminated the alkyne first, which led directly to [Cp* 2 Ti(NC 2 Ph 2 ) 2 ] ( 6 ) with two keteniminate ligands. In contrast, the reaction of 2 b with diphenylacetonitrile involved a formal coupling of the nitriles to obtain the unusual four‐membered titanacycle 7 . An unexpected six‐membered fused zirconaheterocycle ( 8 ) resulted from the reaction of 3 with PhCH 2 CN. The molecular structures of complexes 4 , 5 , 6 , 7 and 8 were determined by X‐ray crystallography." @default.
- W1972070055 created "2016-06-24" @default.
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- W1972070055 date "2013-02-27" @default.
- W1972070055 modified "2023-10-18" @default.
- W1972070055 title "Reactions of Group 4 Metallocene Complexes with Mono- and Diphenylacetonitrile: Formation of Unusual Four- and Six-Membered Metallacycles" @default.
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- W1972070055 doi "https://doi.org/10.1002/chem.201204211" @default.
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