Bulky Chelating Diamide Complexes of Zirconium: Synthesis, Structure, and Reactivity of d0 Alkyl Derivatives
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- 作者：John D. Scollard ; David H. McConville ; and Jagadese J. Vittal
- 刊名：Organometallics
- 出版年：1997
- 出版时间：September 30, 1997
- 年：1997
- 卷：16
- 期：20
- 页码：4415 - 4420
- 全文大小：262K
- 年卷期：v.16,no.20(September 30, 1997)
- ISSN：1520-6041
文摘
The reaction of 2 equiv of LiNHAr (Ar =2,6-iPr2C6H3) with1,3-dibromopropane yieldsthe diamine ArHN(CH2)3NHAr((BAIP)H2, 1). The reaction of(BAIP)H2 withZr(NMe2)4yields the complex (BAIP)Zr(NMe2)2(2) and 2 equiv of NHMe2. Compound2 reacts with 2equiv of [Me2NH2]Cl to yield(BAIP)ZrCl2(NHMe2)2(3) and in the presence of excess pyridineaffords the complex (BAIP)ZrCl2py2(4). The base-free dichloride complex(BAIP)ZrCl2 (5)can be prepared from 2 and excess ClSiMe3.The alkylation of 4 or 5 with 2 equiv ofMeMgBr,2 equiv of PhCH2MgCl, and 1 equiv of NaCp(DME)yields the alkyl derivatives (BAIP)ZrR2(6a, R = Me; 6b, R = CH2Ph)and (BAIP)Zr(
5-C5H5)Cl(8), respectively. The reaction of 2equiv of PhMe2CCH2MgCl with complex4 yields the 2-pyridyl complex(BAIP)Zr(2-N,C-NC5H4)(CH2CMe2Ph)(7). An X-ray study of 7 revealed a cappedtetrahedron geometry withthe pyridyl nitrogen occupying the capping position. Complex7 is likely formed via protonabstraction from coordinated pyridine. The catalyst system6a/MAO polymerizes 1-hexeneto a mixture of high polymer and oligomers. Activation with{Ph3C}[B(C6F5)4]yields onlyoligomers (n = 2-7). Rapid 
le">-hydride eliminationprecludes polymer formation in thesesystems.
5-C5H5)Cl(8), respectively. The reaction of 2equiv of PhMe2CCH2MgCl with complex4 yields the 2-pyridyl complex(BAIP)Zr(2-N,C-NC5H4)(CH2CMe2Ph)(7). An X-ray study of 7 revealed a cappedtetrahedron geometry withthe pyridyl nitrogen occupying the capping position. Complex7 is likely formed via protonabstraction from coordinated pyridine. The catalyst system6a/MAO polymerizes 1-hexeneto a mixture of high polymer and oligomers. Activation with{Ph3C}[B(C6F5)4]yields onlyoligomers (n = 2-7). Rapid le">-hydride eliminationprecludes polymer formation in thesesystems.