期刊
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
卷 54, 期 24, 页码 7068-7072出版社
WILEY-V C H VERLAG GMBH
DOI: 10.1002/anie.201501728
关键词
cyclo-P-5; density functional theory; phosphorus; uranium; delta bonding
资金
- Royal Society
- European Research Council
- Engineering and Physical Sciences Research Council
- University of Nottingham
- University of Manchester
- UK National Nuclear Laboratory
- COST Action [CM1006]
- EPSRC [EP/K024000/1, EP/M027015/1, EP/K024000/2, EP/K038869/1, EP/G051763/1] Funding Source: UKRI
- Engineering and Physical Sciences Research Council [EP/M027015/1, EP/K038869/1, EP/K024000/1, EP/G051763/1, EP/K024000/2] Funding Source: researchfish
Reaction of [U(Tren(TIPS))] [1, Tren(TIPS) = N(CH(2)CH(2)NSiiPr(3))(3)] with 0.25 equivalents of P-4 reproducibly affords the unprecedented actinide inverted sandwich cyclo-P-5 complex [{U(Tren(TIPS))}(2)(mu-eta(5) : eta(5)-cyclo-P-5)] (2). All prior examples of cyclo-P-5 are stabilized by delta-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 sigma -and pi-interactions with minimal delta-bonding, theoretical calculations suggest the principal bonding in the U(P-5) U unit is polarized delta-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 delta-symmetry 5f orbitals.
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