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An Inverted‐Sandwich Diuranium μ‐η 5 :η 5 ‐Cyclo‐P 5 Complex Supported by U‐P 5 δ‐Bonding
Author(s) -
Gardner Benedict M.,
Tuna Floriana,
McInnes Eric J. L.,
McMaster Jonathan,
Lewis William,
Blake Alexander J.,
Liddle Stephen T.
Publication year - 2015
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.201501728
Subject(s) - cyclopentadienyl complex , crystallography , uranium , actinide , charge (physics) , chemistry , ion , acceptor , physics , inorganic chemistry , nuclear physics , biochemistry , organic chemistry , quantum mechanics , condensed matter physics , catalysis
Reaction of [U(Tren TIPS )] [ 1 , Tren TIPS =N(CH 2 CH 2 NSi i Pr 3 ) 3 ] with 0.25 equivalents of P 4 reproducibly affords the unprecedented actinide inverted sandwich cyclo‐P 5 complex [{U(Tren TIPS )} 2 (μ‐η 5 :η 5 ‐cyclo‐P 5 )] ( 2 ). All prior examples of cyclo‐P 5 are stabilized by d‐block metals, so 2 shows that cyclo‐P 5 does not require d‐block ions to be prepared. Although cyclo‐P 5 is isolobal to cyclopentadienyl, which usually bonds to metals via σ‐ and π‐interactions with minimal δ‐bonding, theoretical calculations suggest the principal bonding in the U(P 5 )U unit is polarized δ‐bonding. Surprisingly, the characterization data are overall consistent with charge transfer from uranium to the cyclo‐P 5 unit to give a cyclo‐P 5 charge state that approximates to a dianionic formulation. This is ascribed to the larger size and superior acceptor character of cyclo‐P 5 compared to cyclopentadienyl, the strongly reducing nature of uranium(III), and the availability of uranium δ‐symmetry 5f orbitals.