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.
Light-Driven Ring Slippage in [Re(η7-C7H7)(η5-C7H9)]+ and the Inertness of Its Technetium Homologue / Battistin, F.; Bolliger, R.; Besmer, M. L.; Fox, T.; Blacque, O.; Braband, H.; Alberto, R.. - In: INORGANIC CHEMISTRY. - ISSN 0020-1669. - 63:5(2024), pp. 2701-2708. [10.1021/acs.inorgchem.3c04052]
Light-Driven Ring Slippage in [Re(η7-C7H7)(η5-C7H9)]+ and the Inertness of Its Technetium Homologue
Battistin F.
;Alberto R.
2024-01-01
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.Pubblicazioni consigliate
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