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Stabilization of Pentaphospholes as ?5 -Coordinating Ligands.

ABSTRACT: Electrophilic functionalisation of [Cp*Fe(?5 -P5 )] (1) yields the first transition-metal complexes of pentaphospholes (cyclo-P5 R). Silylation of 1 with [(Et3 Si)2 (?-H)][B(C6 F5 )4 ] leads to the ionic species [Cp*Fe(?5 -P5 SiEt3 )][B(C6 F5 )4 ] (2), whose subsequent reaction with H2 O yields the parent compound [Cp*Fe(?5 -P5 H)][B(C6 F5 )4 ] (3). The synthesis of a carbon-substituted derivative [Cp*Fe(?5 -P5 Me)][X] ([X]- =[FB(C6 F5 )3 ]- (4?a), [B(C6 F5 )4 ]- (4?b)) is achieved by methylation of 1 employing [Me3 O][BF4 ] and B(C6 F5 )3 or a combination of MeOTf and [Li(OEt2 )2 ][B(C6 F5 )4 ]. The structural characterisation of these compounds reveals a slight envelope structure for the cyclo-P5 R ligand. Detailed NMR-spectroscopic studies suggest a highly dynamic behaviour and thus a distinct lability for 2 and 3 in solution. DFT calculations shed light on the electronic structure and bonding situation of this unprecedented class of compounds.

SUBMITTER: Riesinger C 

PROVIDER: S-EPMC7814675 | biostudies-literature | 2020 Dec

REPOSITORIES: biostudies-literature

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Stabilization of Pentaphospholes as η<sup>5</sup> -Coordinating Ligands.

Riesinger Christoph C   Balázs Gábor G   Bodensteiner Michael M   Scheer Manfred M  

Angewandte Chemie (International ed. in English) 20201022 52

Electrophilic functionalisation of [Cp*Fe(η<sup>5</sup> -P<sub>5</sub> )] (1) yields the first transition-metal complexes of pentaphospholes (cyclo-P<sub>5</sub> R). Silylation of 1 with [(Et<sub>3</sub> Si)<sub>2</sub> (μ-H)][B(C<sub>6</sub> F<sub>5</sub> )<sub>4</sub> ] leads to the ionic species [Cp*Fe(η<sup>5</sup> -P<sub>5</sub> SiEt<sub>3</sub> )][B(C<sub>6</sub> F<sub>5</sub> )<sub>4</sub> ] (2), whose subsequent reaction with H<sub>2</sub> O yields the parent compound [Cp*Fe(η<sup>5</sup  ...[more]

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