Spin Distribution in Electron-Rich Piano-Stool Iron(III) Pyridylalkynyl Radical Cations Containing [(η2-dppe)(η5-C5Me5)FeCC]+ End Groups

This experimental and theoretical contribution is aimed at investigating the electronic structure of cationic electron-rich ethynylpyridyl Fe(III) derivatives of the formula [(η2-dppe)(η5-C5Me5)FeCC(x-C5H4N)][PF6] (x = 4, 3, 2; 1a−c[PF6]) and [(η2-dppe)(η5-C5Me5)FeCC(2,5-C5H3NX)][PF6] (X = Cl, Br;...

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Bibliographic Details
Published inOrganometallics Vol. 29; no. 11; pp. 2491 - 2502
Main Authors Paul, Frédéric, Malvolti, Floriane, da Costa, Grégory, Le Stang, Sylvie, Justaud, Frédéric, Argouarch, Gilles, Bondon, Arnaud, Sinbandhit, Sourisak, Costuas, Karine, Toupet, Loic, Lapinte, Claude
Format Journal Article
LanguageEnglish
Published American Chemical Society 14.06.2010
Subjects
Biochemistry
Biochemistry, Molecular Biology
Biophysics
Life Sciences
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ISSN0276-7333
1520-6041
DOI10.1021/om100173x

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Summary:This experimental and theoretical contribution is aimed at investigating the electronic structure of cationic electron-rich ethynylpyridyl Fe(III) derivatives of the formula [(η2-dppe)(η5-C5Me5)FeCC(x-C5H4N)][PF6] (x = 4, 3, 2; 1a−c[PF6]) and [(η2-dppe)(η5-C5Me5)FeCC(2,5-C5H3NX)][PF6] (X = Cl, Br; 2a,b[PF6]). The Mössbauer, NMR, and ESR characterization of these paramagnetic species are reported and discussed in connection with DFT results. Special emphasis is put on the electronic effect of the nitrogen atom and of the halogen substituent on the spin distribution within the pyridyl unit. It is shown that 1H NMR constitutes a straightforward empirical way to investigate the slight changes in spin distribution taking place on the heteroaryl ring.
ISSN:0276-7333
1520-6041
DOI:10.1021/om100173x