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- W2951777781 abstract "The rich chemistry of substituted bis(cyclopentadienyl)zirconium and hafnium complexes bearing side-on coordinated dinitrogen ligands is highlighted in this Perspective. Our studies in this area were initially motivated by the desire to understand side-on vs. end-on dinitrogen coordination in bimetallic zirconocene and hafnocene N2 compounds. In the cases where η2,η2-dinitrogen compounds were isolated, both structural and computational data have established significant imido character in the metal–nitrogen bonds. This additional bonding interaction, which is diminished in end-on complexes bearing both terminal and bridging N2 ligands, facilitates dinitrogen functionalization by non-polar reagents including dihydrogen, carbon–hydrogen bonds and weak Bronsted acids such as water and ethanol. In hafnocene chemistry, where unwanted side-on, end-on isomerization is suppressed, cycloaddition of phenylisocyanate to coordinated N2 has also been accomplished. For N–H bond forming reactions involving H2, kinetic measurements, in addition to isotopic labelling and computational studies, are consistent with dinitrogen functionalization by 1,2-addition involving a highly ordered, four-centred transition structure." @default.
- W2951777781 created "2019-06-27" @default.
- W2951777781 creator A5087910041 @default.
- W2951777781 date "2007-05-01" @default.
- W2951777781 modified "2023-09-23" @default.
- W2951777781 title "Dinitrogen Functionalization with Bis(cyclopentadienyl) Complexes of Zirconium and Hafnium" @default.
- W2951777781 cites W2079467764 @default.
- W2951777781 doi "https://doi.org/10.1002/chin.200718215" @default.
- W2951777781 hasPublicationYear "2007" @default.
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