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An Inverted-Sandwich Diuranium ?-?(5):?(5)-Cyclo-P5 Complex Supported by U-P5 ?-Bonding.

ABSTRACT: Reaction of [U(Tren(TIPS))] [1, Tren(TIPS)=N(CH2CH2NSiiPr3)3] with 0.25?equivalents of P4 reproducibly affords the unprecedented actinide inverted sandwich cyclo-P5 complex [{U(Tren(TIPS))}2(?-?(5):?(5)-cyclo-P5)] (2). All prior examples of cyclo-P5 are stabilized by d-block metals, so 2 shows that cyclo-P5 does not require d-block ions to be prepared. Although cyclo-P5 is isolobal to cyclopentadienyl, which usually bonds to metals via ?- and ?-interactions with minimal ?-bonding, theoretical calculations suggest the principal bonding in the U(P5)U unit is polarized ?-bonding. Surprisingly, the characterization data are overall consistent with charge transfer from uranium to the cyclo-P5 unit to give a cyclo-P5 charge state that approximates to a dianionic formulation. This is ascribed to the larger size and superior acceptor character of cyclo-P5 compared to cyclopentadienyl, the strongly reducing nature of uranium(III), and the availability of uranium ?-symmetry 5f orbitals.

SUBMITTER: Gardner BM 

PROVIDER: S-EPMC4955234 | biostudies-other | 2015 Jun

REPOSITORIES: biostudies-other

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An Inverted-Sandwich Diuranium μ-η<sup>5</sup>:η<sup>5</sup>-Cyclo-P<sub>5</sub> Complex Supported by U-P<sub>5</sub> δ-Bonding.

Gardner Benedict M BM   Tuna Floriana F   McInnes Eric J L EJ   McMaster Jonathan J   Lewis William W   Blake Alexander J AJ   Liddle Stephen T ST  

Angewandte Chemie (Weinheim an der Bergstrasse, Germany) 20150427 24

Reaction of [U(Tren<sup>TIPS</sup>)] [<b>1</b>, Tren<sup>TIPS</sup>=N(CH<sub>2</sub>CH<sub>2</sub>NSi<i>i</i>Pr<sub>3</sub>)<sub>3</sub>] with 0.25 equivalents of P<sub>4</sub> reproducibly affords the unprecedented actinide inverted sandwich cyclo-P<sub>5</sub> complex [{U(Tren<sup>TIPS</sup>)}<sub>2</sub>(μ-η<sup>5</sup>:η<sup>5</sup>-cyclo-P<sub>5</sub>)] (<b>2</b>). All prior examples of cyclo-P<sub>5</sub> are stabilized by d-block metals, so <b>2</b> shows that cyclo-P<sub>5</sub> does not  ...[more]

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