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- W1997751510 endingPage "3555" @default.
- W1997751510 startingPage "3546" @default.
- W1997751510 abstract "A series of amidate-ligated dibenzyl zirconium and hafnium complexes are accessed through protonolysis reactions of the amide proligands 2,6-dimethylphenylpivaloylamide, [DMP(NO)tBu]H (3), and 1,3-bis(1-adamantylamide)-2,2-dimethylpropane, Ad[O2N2]H2 (5), with Zr(CH2Ph)4 or Hf(CH2Ph)4. The resulting dibenzyl complexes [DMP(NO)tBu]2Zr(CH2Ph)2 (4), Ad[O2N2]Zr(CH2Ph)2(THF) (6), and Ad[O2N2]Hf(CH2Ph)2(THF) (7) are structurally characterized. Insertion reactions of 4 with isocyanides are investigated, resulting in the formation of an η2-iminoacyl species, [DMP(NO)tBu]2Zr(η2-2,6-Me2C6H3N═CCH2Ph)2 (8), which undergoes thermal C═C coupling to form an enediamido complex, [DMP(NO)tBu]2Zr(η4-ArNC(CH2Ph)═C(CH2Ph)NAr) (Ar = 2,6-Me2C6H3) (9). Analogous insertion of tBuN≡C into the Zr−C bonds of 4 results in the formation of a vinylamido complex, [DMP(NO)tBu]2Zr(N(tBu)CH═CHPh)2 (10), through a presumed 1,2-hydrogen migration mechanism from an iminoacyl intermediate similar to 8. Complexes 8 and 9 are also structurally characterized." @default.
- W1997751510 created "2016-06-24" @default.
- W1997751510 creator A5011354131 @default.
- W1997751510 creator A5086077605 @default.
- W1997751510 date "2010-07-15" @default.
- W1997751510 modified "2023-10-03" @default.
- W1997751510 title "Synthesis, Structure, and Insertion Reactivity of Zirconium and Hafnium Amidate Benzyl Complexes" @default.
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- W1997751510 doi "https://doi.org/10.1021/om100424j" @default.
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