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Isolation and electronic structures of derivatized manganocene, ferrocene and cobaltocene anions.

ABSTRACT: The discovery of ferrocene nearly 70 years ago marked the genesis of metallocene chemistry. Although the ferrocenium cation was discovered soon afterwards, a derivatized ferrocenium dication was only isolated in 2016 and the monoanion of ferrocene has only been observed in low-temperature electrochemical studies. Here we report the isolation of a derivatized ferrocene anion in the solid state as part of an isostructural family of 3d metallocenates, which consist of anionic complexes of a metal centre (manganese, iron or cobalt) sandwiched between two bulky Cp^ttt ligands (where Cp^ttt is {1,2,4-C₅H₂ ^tBu₃}). These thermally and air-sensitive complexes decompose rapidly above -30 °C; however, we were able to characterize all metallocenates by a wide range of physical techniques and ab initio calculations. These data have allowed us to map the electronic structures of this metallocenate family, including an unexpected high-spin S = 3/2 ground state for the 19e^- derivatized ferrocene anion.

SUBMITTER: Goodwin CAP

PROVIDER: S-EPMC7610420 | biostudies-literature | 2021 Mar

REPOSITORIES: biostudies-literature

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Isolation and electronic structures of derivatized manganocene, ferrocene and cobaltocene anions.

Goodwin Conrad A P CAP Giansiracusa Marcus J MJ Greer Samuel M SM Nicholas Hannah M HM Evans Peter P Vonci Michele M Hill Stephen S Chilton Nicholas F NF Mills David P DP

Nature chemistry 20201214 3

The discovery of ferrocene nearly 70 years ago marked the genesis of metallocene chemistry. Although the ferrocenium cation was discovered soon afterwards, a derivatized ferrocenium dication was only isolated in 2016 and the monoanion of ferrocene has only been observed in low-temperature electrochemical studies. Here we report the isolation of a derivatized ferrocene anion in the solid state as part of an isostructural family of 3d metallocenates, which consist of anionic complexes of a metal c ...[more]

PMID: 33318673

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Project description:Eleven (4-phen-yl)piperazinium salts containing organic anions have been prepared and structurally characterized, namely, 4-phenyl-piperazin-1-ium 4-fluoro-benzoate monohydrate, C10H15N2 +·C7H4FO2 -·H2O, 1; 4-phenyl-piperazin-1-ium 4-bromo-benzoate monohydrate, C10H15N2 +·C7H4BrO2 -·H2O, 3; 4-phenyl-piperazin-1-ium 4-iodo-benzoate, C10H15N2 +·C7H4IO2 -, 4; 4-phenyl-piperazin-1-ium 4-nitro-benzoate, C10H15N2 +·C7H4NO4 -, 5; 4-phenyl-piperazin-1-ium 3,5-di-nitro-salicylate, C10H15N2 +·C7H3N2O7 -, 6; 4-phenyl-piperazin-1-ium 3,5-di-nitro-benzoate, C10H15N2 +·C7H3N2O6 -, 7; 4-phenyl-piperazin-1-ium picrate, C10H15N2 +·C6H2N3O7 -, 8; 4-phenyl-piperazin-1-ium benzoate monohydrate, C10H15N2 +·C7H5O2 -·H2O, 9; 4-phenyl-piperazin-1-ium p-toluene-sulfonate, C10H15N2 +·C7H7O3S-, 10; 4-phenyl-piperazin-1-ium tartarate monohydrate, C10H15N2 +·C4H5O6 -·H2O, 11; and 4-phenyl-piperazin-1-ium fumarate, C10H15N2 +·C4H3O4 -, 12. Compounds 1 and 3-12 are all 1:1 salts with the acid proton transferred to the phenyl-piperaizine basic N atom (the secondary amine) with the exception of 3 where there is disorder in the proton position with it being 68% attached to the base and 32% attached to the acid. Of the structures with similar stoichiometries only 3 and 9 are isomorphous. The 4-phenyl substituent in all cases occupies an equatorial position except for 12 where it is in an axial position. The crystal chosen for structure 7 was refined as a non-merohedral twin. There is disorder in 5, 6, 10 and 11. For both 5 and 6, a nitro group is disordered and was modeled with two equivalent orientations with occupancies of 0.62 (3)/0.38 (3) and 0.690 (11)/0.310 (11), respectively. For 6, 10 and 11, this disorder is associated with the phenyl ring of the phenyl-piperazinium cation with occupancies of 0.687 (10)/0.313 (10), 0.51 (7)/0.49 (7) and 0.611 (13)/389 (13), respectively. For all salts, the packing is dominated by the N-H⋯O hydrogen bonds formed by the cation and anion. In addition, several structures contain C-H⋯π (1, 3, 4, 8, 9, 10, and 12) and aromatic π-π stacking inter-actions (6 and 8) and one structure (5) contains a -NO2⋯π inter-action. For all structures, the Hirshfeld surface fingerprint plots show the expected prominent spikes as a result of the N-H⋯O and O-H⋯O hydrogen bonds.

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Isolation and electronic structures of derivatized manganocene, ferrocene and cobaltocene anions.

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Isolation and electronic structures of derivatized manganocene, ferrocene and cobaltocene anions.

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