The reaction of linear nitriles with transition metal ions M+ (M = Fe, Co, Ni) in the gas phase. Does the back-bonding ability of the metal ions govern the geometry of the RCN/M+ complexes and what is the effect on the oxidative addition of internal CH bonds?

Carlito B Lebrilla, Thomas Drewello, Helmut Schwarz

Research output: Contribution to journal › Article

30 Citations (Scopus)

Abstract

Experimental evidence is presented that RCN/M+ complexes (M = Co, Ni) exhibit practically identical reactivities upon collisional activation in the gas phase, while the analogous RCN/Fe+ systems are distinct. Insertion of the (complexed) transition metal ion M+ into internal CH bonds of linear alkyl nitriles commences for the RCN/Fe+ system with C(8) while, for the RCN/Co+ and RCN/Ni+ species, a trajectory is operative by which insertion occurs already at C(7). This behaviour can be explained by the different bonding situation of the RCN/Fe+ versus RCN/M+ (M = Co, Ni) systems. In the former, the deviation from the linear C-C-N-Fe+ alignment is less pronounced than in the C-C-N-M+ system (M = Co, Ni) with the consequence that CH bonds of the methylene chain closer to the functional group add oxidatively to the metal ion for M = Co, Ni. Some analogies with the recently described metal-silylene system are discussed.

Original languageEnglish (US)
Pages (from-to)287-294
Number of pages8
JournalInternational Journal of Mass Spectrometry and Ion Processes
Volume79
Issue number3
DOIs
StatePublished - Nov 25 1987
Externally publishedYes

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Nitriles
nitriles
Transition metals
Metal ions
insertion
metal ions
Gases
transition metals
methylidyne
vapor phases
Geometry
geometry
methylene
Functional groups
reactivity
Metals
Chemical activation
alignment
Trajectories
trajectories

ASJC Scopus subject areas

  • Spectroscopy

Cite this

The reaction of linear nitriles with transition metal ions M+ (M = Fe, Co, Ni) in the gas phase. Does the back-bonding ability of the metal ions govern the geometry of the RCN/M+ complexes and what is the effect on the oxidative addition of internal CH bonds? / Lebrilla, Carlito B; Drewello, Thomas; Schwarz, Helmut.

In: International Journal of Mass Spectrometry and Ion Processes, Vol. 79, No. 3, 25.11.1987, p. 287-294.

Research output: Contribution to journal › Article

Lebrilla, CB, Drewello, T & Schwarz, H 1987, 'The reaction of linear nitriles with transition metal ions M+ (M = Fe, Co, Ni) in the gas phase. Does the back-bonding ability of the metal ions govern the geometry of the RCN/M+ complexes and what is the effect on the oxidative addition of internal CH bonds?', International Journal of Mass Spectrometry and Ion Processes, vol. 79, no. 3, pp. 287-294. https://doi.org/10.1016/0168-1176(87)83006-9
Lebrilla CB, Drewello T, Schwarz H. The reaction of linear nitriles with transition metal ions M+ (M = Fe, Co, Ni) in the gas phase. Does the back-bonding ability of the metal ions govern the geometry of the RCN/M+ complexes and what is the effect on the oxidative addition of internal CH bonds? International Journal of Mass Spectrometry and Ion Processes. 1987 Nov 25;79(3):287-294. https://doi.org/10.1016/0168-1176(87)83006-9
Lebrilla, Carlito B ; Drewello, Thomas ; Schwarz, Helmut. / The reaction of linear nitriles with transition metal ions M+ (M = Fe, Co, Ni) in the gas phase. Does the back-bonding ability of the metal ions govern the geometry of the RCN/M+ complexes and what is the effect on the oxidative addition of internal CH bonds?. In: International Journal of Mass Spectrometry and Ion Processes. 1987 ; Vol. 79, No. 3. pp. 287-294.
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N2 - Experimental evidence is presented that RCN/M+ complexes (M = Co, Ni) exhibit practically identical reactivities upon collisional activation in the gas phase, while the analogous RCN/Fe+ systems are distinct. Insertion of the (complexed) transition metal ion M+ into internal CH bonds of linear alkyl nitriles commences for the RCN/Fe+ system with C(8) while, for the RCN/Co+ and RCN/Ni+ species, a trajectory is operative by which insertion occurs already at C(7). This behaviour can be explained by the different bonding situation of the RCN/Fe+ versus RCN/M+ (M = Co, Ni) systems. In the former, the deviation from the linear C-C-N-Fe+ alignment is less pronounced than in the C-C-N-M+ system (M = Co, Ni) with the consequence that CH bonds of the methylene chain closer to the functional group add oxidatively to the metal ion for M = Co, Ni. Some analogies with the recently described metal-silylene system are discussed.

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