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Synthesis and reactivity of the rhenium fulvene sandwich complex [Re(η6-C5H4CH2)(η6-C6H6)]+


Suremann, Nina F; Meola, Giuseppe; Blacque, Olivier; Braband, Henrik; Alberto, Roger (2020). Synthesis and reactivity of the rhenium fulvene sandwich complex [Re(η6-C5H4CH2)(η6-C6H6)]+. Organometallics, 39(14):2713-2718.

Abstract

We present the synthesis of the first mixed-ring rhenium fulvene sandwich complex, [Re(η6-C5H4CH2)(η6-C6H6)]+, from the respective carbinol precursor [Re(η5-C5H4CH2OH)(η6-C6H6)]. The demanding preparation on the basis of the reactive cross-conjugated π system of the fulvene ligand restricts the synthetic accessibility for such fulvene complexes, and the only pathways elaborated originate from the respective carbinols. In contrast to related systems, a suitable rhenium-containing precursor did not exist hitherto. Recently, we described the synthesis of the mixed-aromatic complex [Re(η5-C5H4CHO)(η6-C6H6)] which gave access to the carbinol complex [Re(η5-C5H4CH2OH)(η6-C6H6)] and the title compound, both described herein. With [Re(η6-C5H4CH2)(η6-C6H6)]+ in hand, the susceptibility of the exocyclic methylidene group of the coordinated pentafulvene to nucleophilic attacks was investigated with a variety of Lewis bases (hydride, cyanide, amide, alkoxide, thiolate, and phosphine moieties). The characteristic NMR pattern and X-ray crystal structures of [Re(η6-C5H4CH2)(η6-C6H6)]+ and postfunctionalized [Re(η5-C5H4CH2R)(η6-C6H6)] complexes are presented to confirm their authenticities.

Abstract

We present the synthesis of the first mixed-ring rhenium fulvene sandwich complex, [Re(η6-C5H4CH2)(η6-C6H6)]+, from the respective carbinol precursor [Re(η5-C5H4CH2OH)(η6-C6H6)]. The demanding preparation on the basis of the reactive cross-conjugated π system of the fulvene ligand restricts the synthetic accessibility for such fulvene complexes, and the only pathways elaborated originate from the respective carbinols. In contrast to related systems, a suitable rhenium-containing precursor did not exist hitherto. Recently, we described the synthesis of the mixed-aromatic complex [Re(η5-C5H4CHO)(η6-C6H6)] which gave access to the carbinol complex [Re(η5-C5H4CH2OH)(η6-C6H6)] and the title compound, both described herein. With [Re(η6-C5H4CH2)(η6-C6H6)]+ in hand, the susceptibility of the exocyclic methylidene group of the coordinated pentafulvene to nucleophilic attacks was investigated with a variety of Lewis bases (hydride, cyanide, amide, alkoxide, thiolate, and phosphine moieties). The characteristic NMR pattern and X-ray crystal structures of [Re(η6-C5H4CH2)(η6-C6H6)]+ and postfunctionalized [Re(η5-C5H4CH2R)(η6-C6H6)] complexes are presented to confirm their authenticities.

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Item Type:Journal Article, refereed, original work
Communities & Collections:07 Faculty of Science > Department of Chemistry
Dewey Decimal Classification:540 Chemistry
Scopus Subject Areas:Physical Sciences > Physical and Theoretical Chemistry
Physical Sciences > Organic Chemistry
Physical Sciences > Inorganic Chemistry
Uncontrolled Keywords:Physical and Theoretical Chemistry, Inorganic Chemistry, Organic Chemistry
Language:English
Date:27 July 2020
Deposited On:10 Aug 2020 15:31
Last Modified:11 Aug 2020 20:00
Publisher:American Chemical Society (ACS)
ISSN:0276-7333
OA Status:Green
Publisher DOI:https://doi.org/10.1021/acs.organomet.0c00313

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