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 journalArticle

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

Fingerprint

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

@article{9ec0d23cc2c0418fb8465be8c5010775,
title = "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?",
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.",
author = "Lebrilla, {Carlito B} and Thomas Drewello and Helmut Schwarz",
year = "1987",
month = "11",
day = "25",
doi = "10.1016/0168-1176(87)83006-9",
language = "English (US)",
volume = "79",
pages = "287--294",
journal = "International Journal of Mass Spectrometry",
issn = "1387-3806",
publisher = "Elsevier",
number = "3",

}

TY - JOUR

T1 - 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?

AU - Lebrilla, Carlito B

AU - Drewello, Thomas

AU - Schwarz, Helmut

PY - 1987/11/25

Y1 - 1987/11/25

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.

AB - 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.

UR - http://www.scopus.com/inward/record.url?scp=0642275765&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=0642275765&partnerID=8YFLogxK

U2 - 10.1016/0168-1176(87)83006-9

DO - 10.1016/0168-1176(87)83006-9

M3 - Article

VL - 79

SP - 287

EP - 294

JO - International Journal of Mass Spectrometry

JF - International Journal of Mass Spectrometry

SN - 1387-3806

IS - 3

ER -