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Vibrational spectra and structure of “staircase” carbonyl π-complexes of transition metals

1. Electronic effects

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FTIR spectra have been studied for “staircase” cyclopentadienyl complexes comprising two or three metal carbonyl fragments bound by the metal-carbon bond Cp(CO)2Fe-CpmMn(CO)3 (1), Cp(CO)2Fe-CpmFe(CO)2CH2Ph (2), Cp(CO)2Fe-Cpm(CO)2Fe-CpmMn(CO)3 (3), Cp(CO)2Mo-Cpm(CO)2Fe-CpmMn(CO)3 (4), Cp(CO)3W- Cpm(CO)2Fe-CpmMn(CO)3 (5), Cp(CO)2Fe-Cpm(CO)2Fe-BmCr(CO)3 (6), Cr(CO)3Bm-CpmFe(CO)2CH2Ph (7), where Cp = η5-C5H5, Cpm = η1∶η5-C5H4, Bm = η1∶η6-C6H5, as well as mononuclear model complexes Cp(CO)2Fe(CH)2Ph (8), CpMn(CO)3 (9), and (η6-C6H6)Cr(CO)3 (10). The spectra were interpreted on the basis of the local symmetry of each metal carbonyl center. The positions of vCOs are determined by the mutual electronic effect of each center. CpmM(CO)n groups are strong electron acceptors and cause an increase in vCOs of adjacent M(CO)n groups. Cp(CO)nM groups, being electron donors, cause a decrease in the frequencies of neighboring groups. In trinuclear complexes, the frequencies of the central Fe(CO)2 group are not changed much due to the compensation of donor and acceptor influences of two neighboring substituents.

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Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 11, pp. 1948–1951, November, 1994.

This project was supported by the Russian Foundation for Basic Research (project code No. 93-03-18592).

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Ezernitskaya, M.G., Lokshin, B.V., Orlova, T.Y. et al. Vibrational spectra and structure of “staircase” carbonyl π-complexes of transition metals. Russ Chem Bull 43, 1837–1840 (1994). https://doi.org/10.1007/BF00696312

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Key words

  • infrared spectra
  • π-complexes
  • metal carbonyls
  • electronic effects of substituents