Diverse coordination behaviors of the silyl-linked bis(amidinate) ligand [SiMe2{NC(Ph)N(Ph)}(2)](2-) to zirconium center

The reactions between the silyl-linked bis(amidinate) ligand [SiMe2{NC(Ph)N(Ph)Li(thf)(2)}(2)] and ZrCl4 in different stoichiometric chemistry, 2:1. 1:1, and 1:2, were explored. The resulting zirconium compounds, 1, 2, and 3, showed different molecular structural features which were confirmed by X-r...

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Published inPolyhedron Vol. 29; no. 1; pp. 262 - 269
Main Authors Bai, Sheng-Di, Tong, Hong-Bo, Guo, Jian-Ping, Zhou, Mei-Su, Liu, Dian-Sheng, Yuan, Shi-Fang
Format Journal Article
LanguageEnglish
Published OXFORD Elsevier 13.01.2010
Subjects
Chemistry
Chemistry, Inorganic & Nuclear
Crystallography
Physical Sciences
Science & Technology
Bis(amidinate)
AMIDINATE LIGANDS
ALKYL DERIVATIVES
LOW-VALENT CHEMISTRY
Silyl-linked
STRUCTURAL-CHARACTERIZATION
BOND-CLEAVAGE
HIGHLY EFFICIENT
Zirconium
CHAIN-TRANSFER POLYMERIZATION
BENZAMIDINATE LIGANDS
CATALYTIC-PROPERTIES
Tris(amidinate)
MOLECULAR-STRUCTURES
Rearrangement
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Summary:The reactions between the silyl-linked bis(amidinate) ligand [SiMe2{NC(Ph)N(Ph)Li(thf)(2)}(2)] and ZrCl4 in different stoichiometric chemistry, 2:1. 1:1, and 1:2, were explored. The resulting zirconium compounds, 1, 2, and 3, showed different molecular structural features which were confirmed by X-ray crystallographic analysis. The metal center in I was located in a highly saturated coordination environment with four amidinate moieties. Compound 2 exhibited an unprecedented linked tris(amidinate) N-C-N-Si-N-C-N-Si-N-C-N skeleton formed after the intermolecular rearrangement. In compound 3, a novel silyl-linked imino-amidinate ligand via the intramolecular rearrangement was involved. The mechanism for the formation Of Compounds 2 and 3 was proposed. Compound 2 was found to be a highly active catalyst for ethylene polymerization in the presence of methylalumoxane (MAO). (C) 2009 Elsevier Ltd. All rights reserved.
ISSN:0277-5387
DOI:10.1016/j.poly.2009.08.029