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Stable Salts of Heteroleptic Iron Carbonyl/Nitrosyl Cations.

ABSTRACT: The oxidation of Fe(CO)₅ with the [NO]⁺ salt of the weakly coordinating perfluoroalkoxyaluminate anion [F-{Al(OR^F )₃ }₂ ]^- (R^F =C(CF₃ )₃ ) leads to stable salts of the 18?valence electron (VE) species [Fe(CO)₄ (NO)]⁺ and [Fe(CO)(NO)₃ ]⁺ with the Enemark-Feltham numbers of {FeNO}⁸ and {FeNO}¹⁰ . This finally concludes the triad of heteroleptic iron carbonyl/nitrosyl complexes, since the first discovery of the anionic ([Fe(CO)₃ (NO)]^- ) and neutral ([Fe(CO)₂ (NO)₂ ]) species over 80?years ago. Both complexes were fully characterized (IR, Raman, NMR, UV/Vis, scXRD, pXRD) and are stable at room temperature under inert conditions over months and may serve as useful starting materials for further investigations.

SUBMITTER: Bohnenberger J

PROVIDER: S-EPMC7154531 | biostudies-literature | 2020 Mar

REPOSITORIES: biostudies-literature

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Stable Salts of Heteroleptic Iron Carbonyl/Nitrosyl Cations.

Bohnenberger Jan J Krossing Ingo I

Angewandte Chemie (International ed. in English) 20200124 14

The oxidation of Fe(CO)5 with the [NO]+ salt of the weakly coordinating perfluoroalkoxyaluminate anion [F-{Al(ORF )3 }2 ]- (RF =C(CF3 )3 ) leads to stable salts of the 18 valence electron (VE) species [Fe(CO)4 (NO)]+ and [Fe(CO)(NO)3 ]+ with the Enemark-Feltham numbers of {FeNO}8 and {FeNO}10 . This finally concludes the triad of het ...[more]

PMID: 31846555

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Project description:We use quantitative experimental and theoretical approaches to characterize the vibrational dynamics of the Fe atom in porphyrins designed to model heme protein active sites. Nuclear resonance vibrational spectroscopy (NRVS) yields frequencies, amplitudes, and directions for 57Fe vibrations in a series of ferrous nitrosyl porphyrins, which provide a benchmark for evaluation of quantum chemical vibrational calculations. Detailed normal mode predictions result from DFT calculations on ferrous nitrosyl tetraphenylporphyrin Fe(TPP)(NO), its cation [Fe(TPP)(NO)]+, and ferrous nitrosyl porphine Fe(P)(NO). Differing functionals lead to significant variability in the predicted Fe-NO bond length and frequency for Fe(TPP)(NO). Otherwise, quantitative comparison of calculated and measured Fe dynamics on an absolute scale reveals good overall agreement, suggesting that DFT calculations provide a reliable guide to the character of observed Fe vibrational modes. These include a series of modes involving Fe motion in the plane of the porphyrin, which are rarely identified using infrared and Raman spectroscopies. The NO binding geometry breaks the four-fold symmetry of the Fe environment, and the resulting frequency splittings of the in-plane modes predicted for Fe(TPP)(NO) agree with observations. In contrast to expectations of a simple three-body model, mode energy remains localized on the FeNO fragment for only two modes, an N-O stretch and a mode with mixed Fe-NO stretch and FeNO bend character. Bending of the FeNO unit also contributes to several of the in-plane modes, but no primary FeNO bending mode is identified for Fe(TPP)(NO). Vibrations associated with hindered rotation of the NO and heme doming are predicted at low frequencies, where Fe motion perpendicular to the heme is identified experimentally at 73 and 128 cm-1. Identification of the latter two modes is a crucial first step toward quantifying the reactive energetics of Fe porphyrins and heme proteins.

Dataset Information

Stable Salts of Heteroleptic Iron Carbonyl/Nitrosyl Cations.

Publications

Stable Salts of Heteroleptic Iron Carbonyl/Nitrosyl Cations.

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