Please use this identifier to cite or link to this item: https://doi.org/10.1021/om900142c
Title: Ancillary ligand and ketone substituent effects on the rate of ketone insertion into Zr-C bonds of zirconocene-l-Aza-l,3-diene complexes
Authors: Zhang, J.
Krause, J.A.
Huang, K.-W. 
Guan, H.
Issue Date: 25-May-2009
Citation: Zhang, J., Krause, J.A., Huang, K.-W., Guan, H. (2009-05-25). Ancillary ligand and ketone substituent effects on the rate of ketone insertion into Zr-C bonds of zirconocene-l-Aza-l,3-diene complexes. Organometallics 28 (10) : 2938-2946. ScholarBank@NUS Repository. https://doi.org/10.1021/om900142c
Abstract: Zirconocene-l-aza-l,3-diene complexes, [Me 2Si(C 5H 4) 2]Zr[N(Ar)CH=CHCH(Ph)] (Ar = Ph, 2a; Ar = /J-MeOC 5H 4, 2b) and Cp 2Zr[N(Ar)CH=CHCH(Ph)] (Ar = Ph, 3a; Ar = p-MeOC 6H 4, 3b), have been synthesized and characterized by NMR spectroscopy. X-ray crystal structure determinations of compounds 2a and 3a,b reveal folded five-membered-ring moieties for the zirconacycles. DFT calculations and variable-temperature NMR experiments for complex 2a establish a rapid ring-flipping process at room temperature, with the conformation bearing a pseudoequatorial Ph group more stable by 5.6 kcal/mol. Kinetic studies on ketone insertion into these zirconocene complexes show second-order reactions, and the insertion is more favorable in the presence of a [Me 2Si] ansa bridge, a less electron-rich substituent on the nitrogen, and a more basic ketone. One of the insertion products, namely Cp 2Zr[N(Ph)CH=CHCH(Ph)CPh 2O] (5a), has also been characterized by X-ray crystallography. © 2009 American Chemical Society.
Source Title: Organometallics
URI: http://scholarbank.nus.edu.sg/handle/10635/93103
ISSN: 02767333
DOI: 10.1021/om900142c
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