The coordination of bare Fe+ to aliphatic isonitriles differs from that of Fe+ and nitriles

Karsten Eller, Carlito B Lebrilla, Thomas Drewello, Helmut Schwarz

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Abstract

Circumstantial evidence is presented which suggests that both side-on and end-on complexes are formed in the reactions of aliphatic, unbranched isonitriles RNC (R = C2H5-n-C6H13) with Fe+ in the gas phase. Depending on the chain length of the alkyl groups, two distinct processes are observed for either complexes upon collisional activation. One corresponds to oxidative addition of CH/CC bonds in the vicinity of the functional group to eventually cleave the R-NC bond (R = alkyl). This reaction, which is not observed for isomeric RCN/Fe+ complexes, dominates for R = C2H5-C4H9 and is caused by a side-on complexation of the RNC triple bond. For isonitriles with R = C5H11 and C6H13, this process is still operative; the major reaction, however, corresponds to H2 loss which is shown to involve functionalization of remote CH bonds, as has been demonstrated earlier for RCN/M+ complexes (M = Fe, Co, Ni). The experimental data further suggest that the binding energy of side-on complexes is larger for RNC/Fe+ than for RCN/Fe+. Metal ion induced isomerization of the type RNC → RCN does not seem to occur in the gas phase.

Original languageEnglish (US)
Pages (from-to)3068-3071
Number of pages4
JournalJournal of the American Chemical Society
Volume110
Issue number10
StatePublished - 1988
Externally publishedYes

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Nitriles
Gases
Isomerization
Complexation
Binding energy
Chain length
Functional groups
Metal ions
Metals
Chemical activation
Ions

ASJC Scopus subject areas

  • Chemistry(all)

Cite this

Eller, K., Lebrilla, C. B., Drewello, T., & Schwarz, H. (1988). The coordination of bare Fe+ to aliphatic isonitriles differs from that of Fe+ and nitriles. Journal of the American Chemical Society, 110(10), 3068-3071.

The coordination of bare Fe+ to aliphatic isonitriles differs from that of Fe+ and nitriles. / Eller, Karsten; Lebrilla, Carlito B; Drewello, Thomas; Schwarz, Helmut.

In: Journal of the American Chemical Society, Vol. 110, No. 10, 1988, p. 3068-3071.

Research output: Contribution to journalArticle

Eller, K, Lebrilla, CB, Drewello, T & Schwarz, H 1988, 'The coordination of bare Fe+ to aliphatic isonitriles differs from that of Fe+ and nitriles', Journal of the American Chemical Society, vol. 110, no. 10, pp. 3068-3071.
Eller, Karsten ; Lebrilla, Carlito B ; Drewello, Thomas ; Schwarz, Helmut. / The coordination of bare Fe+ to aliphatic isonitriles differs from that of Fe+ and nitriles. In: Journal of the American Chemical Society. 1988 ; Vol. 110, No. 10. pp. 3068-3071.
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N2 - Circumstantial evidence is presented which suggests that both side-on and end-on complexes are formed in the reactions of aliphatic, unbranched isonitriles RNC (R = C2H5-n-C6H13) with Fe+ in the gas phase. Depending on the chain length of the alkyl groups, two distinct processes are observed for either complexes upon collisional activation. One corresponds to oxidative addition of CH/CC bonds in the vicinity of the functional group to eventually cleave the R-NC bond (R = alkyl). This reaction, which is not observed for isomeric RCN/Fe+ complexes, dominates for R = C2H5-C4H9 and is caused by a side-on complexation of the RNC triple bond. For isonitriles with R = C5H11 and C6H13, this process is still operative; the major reaction, however, corresponds to H2 loss which is shown to involve functionalization of remote CH bonds, as has been demonstrated earlier for RCN/M+ complexes (M = Fe, Co, Ni). The experimental data further suggest that the binding energy of side-on complexes is larger for RNC/Fe+ than for RCN/Fe+. Metal ion induced isomerization of the type RNC → RCN does not seem to occur in the gas phase.

AB - Circumstantial evidence is presented which suggests that both side-on and end-on complexes are formed in the reactions of aliphatic, unbranched isonitriles RNC (R = C2H5-n-C6H13) with Fe+ in the gas phase. Depending on the chain length of the alkyl groups, two distinct processes are observed for either complexes upon collisional activation. One corresponds to oxidative addition of CH/CC bonds in the vicinity of the functional group to eventually cleave the R-NC bond (R = alkyl). This reaction, which is not observed for isomeric RCN/Fe+ complexes, dominates for R = C2H5-C4H9 and is caused by a side-on complexation of the RNC triple bond. For isonitriles with R = C5H11 and C6H13, this process is still operative; the major reaction, however, corresponds to H2 loss which is shown to involve functionalization of remote CH bonds, as has been demonstrated earlier for RCN/M+ complexes (M = Fe, Co, Ni). The experimental data further suggest that the binding energy of side-on complexes is larger for RNC/Fe+ than for RCN/Fe+. Metal ion induced isomerization of the type RNC → RCN does not seem to occur in the gas phase.

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