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An Inverted-Sandwich Diuranium mu - eta super(5): eta super( 5)-Cyclo-P sub(5) Complex Supported by U-P sub(5) delta -Bonding

Reaction of [U(Tren super(TIPS))] [1, Tren super(TIPS)=N(CH sub(2)CH sub(2)NSiiPr sub(3)) sub(3)] with 0.25equivalents of P sub(4) reproducibly affords the unprecedented actinide inverted sandwich cyclo-P sub(5) complex [{U(Tren super(TIPS))} sub(2)( mu - eta super(5): eta super(5)-cyclo-P sub(5))]... Full description

Journal Title: Angewandte Chemie (International Edition) Jun 2015, Vol.54(24), pp.7068-7072
Main Author: Gardner, Benedict
Other Authors: Tuna, Floriana , Mcinnes, Eric , Mcmaster, Jonathan , Lewis, William , Blake, Alexander , Liddle, Stephen
Format: Electronic Article Electronic Article
Language: English
Subjects:
ID: ISSN: 1433-7851 ; E-ISSN: 1521-3773 ; DOI: 10.1002/anie.201501728
Link: http://search.proquest.com/docview/1700983045/?pq-origsite=primo
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title: An Inverted-Sandwich Diuranium mu - eta super(5): eta super( 5)-Cyclo-P sub(5) Complex Supported by U-P sub(5) delta -Bonding
format: Article
creator:
  • Gardner, Benedict
  • Tuna, Floriana
  • Mcinnes, Eric
  • Mcmaster, Jonathan
  • Lewis, William
  • Blake, Alexander
  • Liddle, Stephen
subjects:
  • Availability
  • Uranium
  • Formulations
  • Bonding
  • Charge Transfer
  • Charge
  • Approximation
  • Mathematical Analysis
  • Actinides
  • Analysis (MD)
  • Chemical Analysis (Ep)
  • Chemical Analysis (Ed)
  • Chemical Analysis (EC)
ispartof: Angewandte Chemie (International Edition), Jun 2015, Vol.54(24), pp.7068-7072
description: Reaction of [U(Tren super(TIPS))] [1, Tren super(TIPS)=N(CH sub(2)CH sub(2)NSiiPr sub(3)) sub(3)] with 0.25equivalents of P sub(4) reproducibly affords the unprecedented actinide inverted sandwich cyclo-P sub(5) complex [{U(Tren super(TIPS))} sub(2)( mu - eta super(5): eta super(5)-cyclo-P sub(5))] (2). All prior examples of cyclo-P sub(5) are stabilized by d-block metals, so 2 shows that cyclo-P sub(5) does not require d-block ions to be prepared. Although cyclo-P sub(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 sub(5))U unit is polarized delta -bonding. Surprisingly, the characterization data are overall consistent with charge transfer from uranium to the cyclo-P sub(5) unit to give a cyclo-P sub(5) charge state that approximates to a dianionic formulation. This is ascribed to the larger size and superior acceptor character of cyclo-P sub(5) compared to cyclopentadienyl, the strongly reducing nature of uranium(III), and the availability of uranium delta -symmetry 5f orbitals. Not your everyday sandwich: Reaction of 1 with P sub(4) affords the unprecedented actinide inverted-sandwich cyclo-P sub(5) complex 2. Theoretical calculations suggest the principal bonding in the U(P sub(5))U unit is two polarized delta -bonds, and combined characterization data suggest charge transfer from uranium to the cyclo-P sub(5) unit to give a cyclo-P sub(5) charge state that approximates to a dianion.
language: eng
source:
identifier: ISSN: 1433-7851 ; E-ISSN: 1521-3773 ; DOI: 10.1002/anie.201501728
fulltext: fulltext
issn:
  • 14337851
  • 1433-7851
  • 15213773
  • 1521-3773
url: Link


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titleAn Inverted-Sandwich Diuranium mu - eta super(5): eta super( 5)-Cyclo-P sub(5) Complex Supported by U-P sub(5) delta -Bonding
creatorGardner, Benedict ; Tuna, Floriana ; Mcinnes, Eric ; Mcmaster, Jonathan ; Lewis, William ; Blake, Alexander ; Liddle, Stephen
contributorGardner, Benedict (correspondence author)
ispartofAngewandte Chemie (International Edition), Jun 2015, Vol.54(24), pp.7068-7072
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subjectAvailability ; Uranium ; Formulations ; Bonding ; Charge Transfer ; Charge ; Approximation ; Mathematical Analysis ; Actinides ; Analysis (MD) ; Chemical Analysis (Ep) ; Chemical Analysis (Ed) ; Chemical Analysis (EC)
descriptionReaction of [U(Tren super(TIPS))] [1, Tren super(TIPS)=N(CH sub(2)CH sub(2)NSiiPr sub(3)) sub(3)] with 0.25equivalents of P sub(4) reproducibly affords the unprecedented actinide inverted sandwich cyclo-P sub(5) complex [{U(Tren super(TIPS))} sub(2)( mu - eta super(5): eta super(5)-cyclo-P sub(5))] (2). All prior examples of cyclo-P sub(5) are stabilized by d-block metals, so 2 shows that cyclo-P sub(5) does not require d-block ions to be prepared. Although cyclo-P sub(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 sub(5))U unit is polarized delta -bonding. Surprisingly, the characterization data are overall consistent with charge transfer from uranium to the cyclo-P sub(5) unit to give a cyclo-P sub(5) charge state that approximates to a dianionic formulation. This is ascribed to the larger size and superior acceptor character of cyclo-P sub(5) compared to cyclopentadienyl, the strongly reducing nature of uranium(III), and the availability of uranium delta -symmetry 5f orbitals. Not your everyday sandwich: Reaction of 1 with P sub(4) affords the unprecedented actinide inverted-sandwich cyclo-P sub(5) complex 2. Theoretical calculations suggest the principal bonding in the U(P sub(5))U unit is two polarized delta -bonds, and combined characterization data suggest charge transfer from uranium to the cyclo-P sub(5) unit to give a cyclo-P sub(5) charge state that approximates to a dianion.
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titleAn Inverted-Sandwich Diuranium mu - eta super(5): eta super( 5)-Cyclo-P sub(5) Complex Supported by U-P sub(5) delta -Bonding
descriptionReaction of [U(Tren super(TIPS))] [1, Tren super(TIPS)=N(CH sub(2)CH sub(2)NSiiPr sub(3)) sub(3)] with 0.25equivalents of P sub(4) reproducibly affords the unprecedented actinide inverted sandwich cyclo-P sub(5) complex [{U(Tren super(TIPS))} sub(2)( mu - eta super(5): eta super(5)-cyclo-P sub(5))] (2). All prior examples of cyclo-P sub(5) are stabilized by d-block metals, so 2 shows that cyclo-P sub(5) does not require d-block ions to be prepared. Although cyclo-P sub(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 sub(5))U unit is polarized delta -bonding. Surprisingly, the characterization data are overall consistent with charge transfer from uranium to the cyclo-P sub(5) unit to give a cyclo-P sub(5) charge state that approximates to a dianionic formulation. This is ascribed to the larger size and superior acceptor character of cyclo-P sub(5) compared to cyclopentadienyl, the strongly reducing nature of uranium(III), and the availability of uranium delta -symmetry 5f orbitals. Not your everyday sandwich: Reaction of 1 with P sub(4) affords the unprecedented actinide inverted-sandwich cyclo-P sub(5) complex 2. Theoretical calculations suggest the principal bonding in the U(P sub(5))U unit is two polarized delta -bonds, and combined characterization data suggest charge transfer from uranium to the cyclo-P sub(5) unit to give a cyclo-P sub(5) charge state that approximates to a dianion.
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titleAn Inverted-Sandwich Diuranium mu - eta super(5): eta super( 5)-Cyclo-P sub(5) Complex Supported by U-P sub(5) delta -Bonding
authorGardner, Benedict ; Tuna, Floriana ; Mcinnes, Eric ; Mcmaster, Jonathan ; Lewis, William ; Blake, Alexander ; Liddle, Stephen
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abstractReaction of [U(Tren super(TIPS))] [1, Tren super(TIPS)=N(CH sub(2)CH sub(2)NSiiPr sub(3)) sub(3)] with 0.25equivalents of P sub(4) reproducibly affords the unprecedented actinide inverted sandwich cyclo-P sub(5) complex [{U(Tren super(TIPS))} sub(2)( mu - eta super(5): eta super(5)-cyclo-P sub(5))] (2). All prior examples of cyclo-P sub(5) are stabilized by d-block metals, so 2 shows that cyclo-P sub(5) does not require d-block ions to be prepared. Although cyclo-P sub(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 sub(5))U unit is polarized delta -bonding. Surprisingly, the characterization data are overall consistent with charge transfer from uranium to the cyclo-P sub(5) unit to give a cyclo-P sub(5) charge state that approximates to a dianionic formulation. This is ascribed to the larger size and superior acceptor character of cyclo-P sub(5) compared to cyclopentadienyl, the strongly reducing nature of uranium(III), and the availability of uranium delta -symmetry 5f orbitals. Not your everyday sandwich: Reaction of 1 with P sub(4) affords the unprecedented actinide inverted-sandwich cyclo-P sub(5) complex 2. Theoretical calculations suggest the principal bonding in the U(P sub(5))U unit is two polarized delta -bonds, and combined characterization data suggest charge transfer from uranium to the cyclo-P sub(5) unit to give a cyclo-P sub(5) charge state that approximates to a dianion.
doi10.1002/anie.201501728
urlhttp://search.proquest.com/docview/1700983045/
date2015-06-08