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Light-Driven Ring Slippage in [Re(η7-C7H7)(η5-C7H9)]+ and the Inertness of Its Technetium Homologue.


ABSTRACT: Here, we present the light-driven reactions of [Re(η7-C7H7)(η5-C7H9)]+ (1+) with nitriles, phosphines, and isocyanides, which are added to 1+ via a ring slippage of the tropylium cation from η7 to η3, forming [Re(η3-C7H7)(η5-C7H9)(L)2]+ (L= acetonitrile 2+; 2-phenylacetonitrile 3+; 1,3,5-triaza-5-phosphoadamantane (PTA) 4+; tert-butyl isocyanide 6+; benzyl isocyanide 7+) and [Re(η3-C7H7)(η5-C7H9)(L)]+ with L = (ethane-1,2-diyl)bis(diphenylphosphane) (dppe) 5+. To compare the reactivities of rhenium and technetium, we also investigated the synthesis of [99Tc(η6-C10H8)2]+, its substitution of naphthalene with cyclohepta-1,3,5-triene to obtain [99Tc(η7-C7H7)(η5-C7H9)]+, and its reactivity (or lack thereof) with light.

SUBMITTER: Battistin F 

PROVIDER: S-EPMC10848200 | biostudies-literature | 2024 Feb

REPOSITORIES: biostudies-literature

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Light-Driven Ring Slippage in [Re(η<sup>7</sup>-C<sub>7</sub>H<sub>7</sub>)(η<sup>5</sup>-C<sub>7</sub>H<sub>9</sub>)]<sup>+</sup> and the Inertness of Its Technetium Homologue.

Battistin Federica F   Bolliger Robin R   Besmer Manuel Luca ML   Fox Thomas T   Blacque Olivier O   Braband Henrik H   Alberto Roger R  

Inorganic chemistry 20240122 5


Here, we present the light-driven reactions of [Re(η<sup>7</sup>-C<sub>7</sub>H<sub>7</sub>)(η<sup>5</sup>-C<sub>7</sub>H<sub>9</sub>)]<sup>+</sup> (<b>1</b><sup>+</sup>) with nitriles, phosphines, and isocyanides, which are added to <b>1</b><sup>+</sup> via a ring slippage of the tropylium cation from η<sup>7</sup> to η<sup>3</sup>, forming [Re(η<sup>3</sup>-C<sub>7</sub>H<sub>7</sub>)(η<sup>5</sup>-C<sub>7</sub>H<sub>9</sub>)(L)<sub>2</sub>]<sup>+</sup> (L= acetonitrile <b>2</b><sup><b>+</b></  ...[more]

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