Preparation and Reactions of Base-FreeBis(1,2,4-tri-tert-butylcyclopentadienyl)uranium Oxide, Cp'2UO

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Reduction of the uranium metallocene,[eta5-1,2,4-(Me3C)3C5H2]2UCl2 (1), Cp'2UCl2, in the presence of2,2'-bipyridyl and sodium naphthalene gives the dark green metallocenecomplex, Cp'2U(bipy) (6), which reacts with p-tolylazide orpyridine-N-oxide to give Cp'2U=N(p-tolyl) (7) or Cp'2U(O)(py) (8),respectively. The Lewis acid, BPh3, precipitates Ph3B(py) and gives thebase-free oxo, Cp'2UO (10), which crystallizes from pentane. Theoxometallocene 10 behaves as a nucleophile with Me3SiX reagents but itdoes not exhibit cycloaddition behavior with acetylenes, suggesting thatthe polar resonance structure, Cp'2U+-O- dominates the double bondresonance structure Cp'2U=O.

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Zi, Guofu; Werkema, Evan L.; Walter, Marc D.; Gottfriedsen,Jochen P. & Andersen, Richard A. May 25, 2005.

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Reduction of the uranium metallocene,[eta5-1,2,4-(Me3C)3C5H2]2UCl2 (1), Cp'2UCl2, in the presence of2,2'-bipyridyl and sodium naphthalene gives the dark green metallocenecomplex, Cp'2U(bipy) (6), which reacts with p-tolylazide orpyridine-N-oxide to give Cp'2U=N(p-tolyl) (7) or Cp'2U(O)(py) (8),respectively. The Lewis acid, BPh3, precipitates Ph3B(py) and gives thebase-free oxo, Cp'2UO (10), which crystallizes from pentane. Theoxometallocene 10 behaves as a nucleophile with Me3SiX reagents but itdoes not exhibit cycloaddition behavior with acetylenes, suggesting thatthe polar resonance structure, Cp'2U+-O- dominates the double bondresonance structure Cp'2U=O.

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  • Journal Name: Organometallics; Journal Volume: 24; Journal Issue: 17; Related Information: Journal Publication Date: August 15,2005

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  • Report No.: LBNL--59364
  • Grant Number: DE-AC02-05CH11231
  • DOI: 10.1021/om050406q | External Link
  • Office of Scientific & Technical Information Report Number: 926470
  • Archival Resource Key: ark:/67531/metadc899744

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  • May 25, 2005

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  • Sept. 27, 2016, 1:39 a.m.

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  • Oct. 31, 2016, 3:55 p.m.

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Zi, Guofu; Werkema, Evan L.; Walter, Marc D.; Gottfriedsen,Jochen P. & Andersen, Richard A. Preparation and Reactions of Base-FreeBis(1,2,4-tri-tert-butylcyclopentadienyl)uranium Oxide, Cp'2UO, article, May 25, 2005; Berkeley, California. (digital.library.unt.edu/ark:/67531/metadc899744/: accessed January 16, 2018), University of North Texas Libraries, Digital Library, digital.library.unt.edu; crediting UNT Libraries Government Documents Department.