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A Rare Uranyl(VI)–Alkyl Ate Complex [Li(DME) 1.5 ] 2 [UO 2 (CH 2 SiMe 3 ) 4 ] and Its Comparison with a Homoleptic Uranium(VI)–Hexaalkyl
Author(s) -
Seaman Lani A.,
Hrobárik Peter,
Schettini Michael F.,
Fortier Skye,
Kaupp Martin,
Hayton Trevor W.
Publication year - 2013
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.201209611
Subject(s) - uranyl , diamagnetism , chemistry , methylene , computer science , crystallography , physics , medicinal chemistry , organic chemistry , ion , quantum mechanics , magnetic field
A rare tetraalkyl–uranyl “ate” complex 1 was prepared and characterized for comparison with a U VI –hexaalkyl complex 2 . Both 1 and 2 feature unprecedented high‐frequency methylene 13 C NMR shifts (see picture). That of complex 2 constitutes a new record for diamagnetic mononuclear complexes. Relativistic DFT calculations show that these extreme shifts are due to spin–orbit effects, a consequence of significant f‐orbital involvement in the UC bond.