[(Allylsilyl)(-amidosilyl)-5-cyclopentadienyl] Group 4 Me
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- 作者：Cristina Ramos ; Pascual Royo ; Maurizio Lanfranchi ; Maria A. Pellinghelli ; Antonio Tiripicchio
- 刊名：Organometallics
- 出版年：2007
- 出版时间：January 15, 2007
- 年：2007
- 卷：26
- 期：2
- 页码：445 - 454
- 全文大小：183K
- 年卷期：v.26,no.2(January 15, 2007)
- ISSN：1520-6041
文摘
Reaction of the dilithium salts Li2{C5H3[1-SiMe2(NR)][3-SiMe2(CH2CH=CH2)]} with TiCl3(THF)3and further oxidation with PbCl2 gave the allylsilyl-substituted 
1-amidosilyl-5-cyclopentadienyltitanium(IV) complexes [Ti{5-C5H3(SiMe2-1-NR)[SiMe2(CH2CH=CH2)]}Cl2] (R = tBu, 1; 2,6-Me2C6H3, 2).Complex 1 was reacted with MeMgCl and (CH2Ph)MgCl to give the dialkyl complexes [Ti{5-C5H3(SiMe2-1-NtBu)[SiMe2(CH2CH=CH2)]}R2] (R = Me, 3; CH2Ph, 4). Reaction of 1 and relatedmonocyclopentadienyl zirconium and hafnium complexes with Na(C5H5) gave the -amidosilyl metallocenederivatives [M(5-C5H5){5-C5H3(SiMe2-1-NtBu)[SiMe2(CH2CH=CH2)]}Cl] (M = Ti, 5; Zr, 6; Hf, 7),which were further methylated with MeMgCl and MeLi to give the methyl derivatives [M(5-C5H5){5-C5H3(SiMe2-1-NtBu)[SiMe2(CH2CH=CH2)]}Me] (M = Ti, 8; Zr, 9). Insertion of CN(2,6-Me2C6H3)into the Zr-Me bond of complex 9 afforded the iminoacyl derivative [Zr(5-C5H5){5-C5H3(SiMe2-1-NtBu)[SiMe2(CH2CH=CH2)]}{1-CMe[N(2,6-Me2C6H3)]}], 10. Methyl abstraction by reaction of theamidosilyl-metallocene compounds 8 and 9 with B(C6F5)3 gave the ionic species [M(5-C5H5){5-C5H3(SiMe2-1-NtBu)[SiMe2(CH2-2-CH=CH2)]}]+[MeB(C6F5)3]- (M = Ti, 11; Zr, 12) stabilized bycoordination of the allyl olefinic moiety, whereas similar benzyl abstraction reactions from the dibenzyl-amidosilyl-monocyclopentadienyl compounds produced further benzyl-migratory insertion of the 2-coordinated olefinic moiety to give the cyclic alkyl complexes [M{5-C5H3(SiMe2-1-NtBu)[SiMe2-CH2-CH(CH2Ph)-CH2]}]+[(CH2Ph)B(C6F5)3]- (M = Zr, 13; Hf, 14). The new compounds werecharacterized by elemental analysis and NMR spectroscopy, and the molecular structures of complexes2, 6, and 7 were determined by X-ray diffraction methods. The chloro complexes 1 and 5-7 were studiedas catalyst precursors in the polymerization of different olefins and the copolymerization of ethylene/1-hexene, after activation with MAO.
1-amidosilyl-5-cyclopentadienyltitanium(IV) complexes [Ti{5-C5H3(SiMe2-1-NR)[SiMe2(CH2CH=CH2)]}Cl2] (R = tBu, 1; 2,6-Me2C6H3, 2).Complex 1 was reacted with MeMgCl and (CH2Ph)MgCl to give the dialkyl complexes [Ti{5-C5H3(SiMe2-1-NtBu)[SiMe2(CH2CH=CH2)]}R2] (R = Me, 3; CH2Ph, 4). Reaction of 1 and relatedmonocyclopentadienyl zirconium and hafnium complexes with Na(C5H5) gave the -amidosilyl metallocenederivatives [M(5-C5H5){5-C5H3(SiMe2-1-NtBu)[SiMe2(CH2CH=CH2)]}Cl] (M = Ti, 5; Zr, 6; Hf, 7),which were further methylated with MeMgCl and MeLi to give the methyl derivatives [M(5-C5H5){5-C5H3(SiMe2-1-NtBu)[SiMe2(CH2CH=CH2)]}Me] (M = Ti, 8; Zr, 9). Insertion of CN(2,6-Me2C6H3)into the Zr-Me bond of complex 9 afforded the iminoacyl derivative [Zr(5-C5H5){5-C5H3(SiMe2-1-NtBu)[SiMe2(CH2CH=CH2)]}{1-CMe[N(2,6-Me2C6H3)]}], 10. Methyl abstraction by reaction of theamidosilyl-metallocene compounds 8 and 9 with B(C6F5)3 gave the ionic species [M(5-C5H5){5-C5H3(SiMe2-1-NtBu)[SiMe2(CH2-2-CH=CH2)]}]+[MeB(C6F5)3]- (M = Ti, 11; Zr, 12) stabilized bycoordination of the allyl olefinic moiety, whereas similar benzyl abstraction reactions from the dibenzyl-amidosilyl-monocyclopentadienyl compounds produced further benzyl-migratory insertion of the 2-coordinated olefinic moiety to give the cyclic alkyl complexes [M{5-C5H3(SiMe2-1-NtBu)[SiMe2-CH2-CH(CH2Ph)-CH2]}]+[(CH2Ph)B(C6F5)3]- (M = Zr, 13; Hf, 14). The new compounds werecharacterized by elemental analysis and NMR spectroscopy, and the molecular structures of complexes2, 6, and 7 were determined by X-ray diffraction methods. The chloro complexes 1 and 5-7 were studiedas catalyst precursors in the polymerization of different olefins and the copolymerization of ethylene/1-hexene, after activation with MAO.