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Transformation of the cyclo‐P5 Middle Deck in [(CpFe)(Cp’’’Co)(μ,η5:η4‐P5)] upon Functionalization – A Comprehensive Study of Reactivity

Dinauer, Sabrina B. ; Piesch, Martin ; Szlosek, Robert ; Seidl, Michael ; Balázs, Gábor ; Scheer, Manfred

Chemistry : a European journal, 2023-06, Vol.29 (32), p.e202300459-n/a [Periódico revisado por pares]

Weinheim: Wiley Subscription Services, Inc

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  • Título:
    Transformation of the cyclo‐P5 Middle Deck in [(CpFe)(Cp’’’Co)(μ,η5:η4‐P5)] upon Functionalization – A Comprehensive Study of Reactivity
  • Autor: Dinauer, Sabrina B. ; Piesch, Martin ; Szlosek, Robert ; Seidl, Michael ; Balázs, Gábor ; Scheer, Manfred
  • Assuntos: Alkali metals ; Chemistry ; Cobalt ; Crystallography ; Decks ; Diamagnetism ; Dimerization ; functionalization ; heterobimetallic complexes ; Iron ; Ligands ; Mass spectrometry ; Mass spectroscopy ; NMR ; Nuclear magnetic resonance ; Nucleophiles ; organophosphorus ligands ; Oxidation ; rearrangement
  • É parte de: Chemistry : a European journal, 2023-06, Vol.29 (32), p.e202300459-n/a
  • Notas: ObjectType-Article-1
    SourceType-Scholarly Journals-1
    ObjectType-Feature-2
    content type line 23
  • Descrição: The heterobimetallic triple‐decker complex [(Cp*Fe)(Cp’’’Co)(μ,η5 : η4‐P5)] (1) was functionalized by main group nucleophiles and subsequently electrophilically quenched or oxidized. Reacting 1 with group 14 nucleophiles revealed different organo‐substituted P5R middle‐decks depending on the steric and electronic effects of the used alkali metal organyls (2: R=tBu; 3: R=Me). Further, with group 15 nucleophiles, the first structural characterized monosubstituted complexes with phosphanides could be obtained as P5 ligands containing exocyclic {PR2} units (4: R=Cy, H; 5: R=Ph). These monoanionic complexes 2–5 were isolated and subsequent electrophilic quenching revealed novel types of neutral functionalized polyphosphorus complexes. These complexes bear formal chains of P5R'R’’ (6: R’=tBu, R’=Me) in a 1,3‐disubstitution pattern or P6R'R’’R’’’ units (7: R’=Cy, R’’=H, R’’’=Me; 8: R’=Me, R’’=Ph, R’’’=Me) in a 1,1,3‐substitution as middle‐decks stabilized by one {Cp’’’Co} and one {Cp*Fe} fragment. One‐electron oxidation of 2, 3 or 5 by AgBF4 gave access to paramagnetic triple‐decker complexes bearing P5R middle‐decks in various coordination fashions (R=tBu (10), R=PPh2 (12)). Interestingly, for R=Me (11), a dimerization is observed revealing a diamagnetic tetranuclear cluster containing a unique dihydrofulvalene‐type P10R2 ligand. All complexes were characterized by crystallographic and spectroscopic methods (EPR, multinuclear NMR and mass spectrometry) and their electronic structures were elucidated by DFT calculations. Various transformations of the initial cyclo‐P5 ligand in the triple‐decker complex [(Cp*Fe)(Cp’’’Co)(μ,η5 : η4‐P5)] show that the reaction with main group nucleophiles yields different products depending on the steric demand of the nucleophile used. Subsequent oxidation/electrophilic quenching provides a plethora of P5R2 and P6R3 organophosphorus ligand complexes in unique 1,3 or 1,4 substitution pattern as opposed to the parent complex [Cp*Fe(η5‐P5)].
  • Editor: Weinheim: Wiley Subscription Services, Inc
  • Idioma: Inglês
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