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Trimethylsilylcyclopentadienyl (Cp ′ ) Uranium Chemistry: Synthetic and Structural Studies of Cp ′ 4 U and Cp ′ 3 U X ( X = Cl, I, Me)
Author(s) -
Windorff Cory J.,
MacDonald Matthew R.,
Ziller Joseph W.,
Evans William J.
Publication year - 2017
Publication title -
zeitschrift für anorganische und allgemeine chemie
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.354
H-Index - 66
eISSN - 1521-3749
pISSN - 0044-2313
DOI - 10.1002/zaac.201700323
Subject(s) - chemistry , cyclopentadienyl complex , crystallography , reagent , crystal structure , stereochemistry , organic chemistry , catalysis
Cp′ 4 U (Cp′ = C 5 H 4 SiMe 3 ) was synthesized from: (a) KCp′ and [Cp′ 3 U(THF)][BPh 4 ]; (b) Cp′ 3 U and Cp′ 2 Pb; and (c) [K(2.2.2‐cryptand)][Cp′ 4 U] and AgBPh 4 . The compound was identified by X‐ray crystallography as a rare example of a structurally‐characterized tetrakis(cyclopentadienyl)U IV complex. For comparison, the corresponding Th complex, Cp′ 4 Th, was isolated from the direct combination of ThBr 4 (THF) 4 with excess KCp′. During the preparation of Cp′ 3 UMe, the precursor of the [Cp′ 3 U(THF)][BPh 4 ] reagent used above, it was discovered that the reaction of Cp′ 3 UCl and MeLi gives a mixture of Cp′ 3 UMe and Cp′ 3 UCl that can co‐crystallize better than Cp′ 3 UMe in pure form. The Cp′ 3 UMe/Cp′ 3 UCl mixture forms single crystals suitable for X‐ray crystallography and provides a new way to characterize the oil, Cp′ 3 UMe. Cp′ 3 UCl and Cp′ 3 UI were also crystallographically characterized for comparison with the Cp′ 3 UMe/Cp′ 3 UCl crystals.