The detailed mechanism for the reaction of bare iron(I) ions with tert-butyl cyanide and isocyanide in the gas phase

Eller, Karsten; Schwarz, Helmut

doi:10.1021/om00109a040

Cited by 26 publications

(8 citation statements)

References 2 publications

(2 reference statements)

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“…It appears that CuCl + activates the C‐H bond of the methylene group resulting in the elimination of HCl, as proposed in Scheme . Similar C‐H activation by bare metal ions is well‐documented in the literature 19…”

Section: Resultssupporting

confidence: 78%

Collision‐induced dissociation of MCl⁺ adducts (M = Mg, Mn, Zn, Co, Ni and Cu) and Cu⁺ and Ag⁺ adducts of dithioalkyl ketene acetals

Madhusudanan

Bhat

Suryawanshi

2001

Rapid Comm Mass Spectrometry

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Electrospray ionization mass spectra of equimolar solutions of dithioalkyl ketene acetals 1 and 2 and metal chlorides (MgCl(2), MnCl(2), ZnCl(2), CoCl(2), NiCl(2) and CuCl(2)) produced abundant ligated metal ion adducts [1 + MCl](+) and [2 + MCl](+). In addition, CuCl(2) also gave rise to Cu(+) adducts. The ligated metal ion adducts upon collision-induced dissociation (CID) showed characteristic fragmentation pathways reflecting the favoured site of coordination. The results show that MgCl(+) prefers oxygen over sulfur, whereas the reverse is true for ZnCl(+) adducts, exemplified by the preferred fragmentation of [1 + MgCl](+) as elimination of MgCl(OH), while that of [1 + ZnCl](+) is expulsion of ZnCl(SCH(3)). Co and Ni chloride adducts tend to give stable metal coordinated species. Cleavage of the dithiolane ring followed by elimination of C(2)H(4)S is the preferred pathway during the CID of [2 + MCl](+) adducts. The CuCl(+) adducts of 1 and 2 showed reduction of Cu((I)) to Cu((0)) resulting in the M(+)(*)ions of 1 and 2. Abstraction of *CH(3) resulting in elimination of CuCH(3) was observed during CID of Cu(+) adducts of 1 and 2. A comparative study of the corresponding Ag(+) adducts revealed a similar behaviour.

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Section: Resultssupporting

confidence: 78%

Collision‐induced dissociation of MCl⁺ adducts (M = Mg, Mn, Zn, Co, Ni and Cu) and Cu⁺ and Ag⁺ adducts of dithioalkyl ketene acetals

Madhusudanan

Bhat

Suryawanshi

2001

Rapid Comm Mass Spectrometry

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“…The elimination of C 2H 4 may also be described in terms of the ion/dipole intermediate, as in the case of o-disubstituted nitriles [16,17). However, this requires an end-on coordination.…”

Section: Methodsmentioning

confidence: 99%

“…In general, the remote functionalization occurs for "end-on" complexes. In addition, two mechanisms, "aiiyiic" and" ion/dipole," are established for a-branched nitriles; the former is based on insertion into C-CN bond/B-H shift/allylic C-C bond cleavage [16], and the latter involves cleavage of C-CN bond forming an ion/dipole complex followed by H transfer and ligand elimination [16,17].…”

mentioning

confidence: 99%

Ion-molecule reaction of alkanenitriles and transition-metal ions in the gas phase: A study on fragmentation mechanism of the adducts

Chen

Miller

1991

J. Am. Soc. Mass Spectrom.

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Gas-phase ion-molecule reactions between transition-metal ions (Mn +, Fe+, Co+, Ni +) and propionitri1e and acetonitrile were investigated. Ion-molecule adducts were prepared in a modified fast atom bombardment source and their metastable and collision-induced fragmentations, occurring in the frrst held-free region of an E/B configuration instrument, were studied by means of B/E linked scans. The experimental data suggest a coexistence of both "end-on" and "side-on" coordination modes; the former undergoes ligand detachment alone, whereas the latter loses methyl and ethyl radicals by insertion of M+ into organic substrates and further produces ethylene via a l3-hydrogen transfer. An order for the bonding energy of RCN-M+ is also suggested: RCN-Ni+> RCN-Co+> RCN-Fe+> RCNMn+.

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“…8. It is well known that isocyanides react easily by the ion/dipole mechanism to form HNC and M(HNC)+ [2] [5] [32]. Unfortunately the intensity of the MC,H,S+ ions was too low to perform CID experiments [33] in order to see, if indeed they possessed a MS(C,H,)+ structure as this mechanism would imply.…”

Section: Methodsmentioning

confidence: 99%

“…+ MC,Hi + HNCS (2) HNCS is obviously much stronger bound than butene, and thus MHNCS' is the predominant product. The complete absence of HNCS loss for the early transition-metal ions Ti+-Cr" is strange, however, and might point to a different mechanism for the MHNCS' formation.…”

Section: M+ + C4hncsmentioning

confidence: 99%

Gas‐Phase Chemistry of Ti⁺ to Zn⁺ with Butyl Isothiocyanate

Eller

Akkök

Schwarz

1991

Helvetica Chimica Acta

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(1 3. IX.91)Using a complete set of 2H-labeled isotopomers, the gas-phase reactions of Ti' to Zn+ with butyl isothiocyanate are studied. The main product for most of the metal ions is MHNCS+ formed by an ion/dipole mechanism. Exceptions are Cr', which yields significant amounts of H, and H,S loss, Mn', which is the only ion that does not form MHNCS' at all but produces mainly C,H, and C3H6, and Zn', which predominantly reacts by charge transfer.Introduction. -Gas-phase organometallic chemistry [ 13 can be used to study the intrinsic properties of bare transition-metal ions. The absence of a solvent shell or counter ions simplifies the analysis and simultaneously makes the 'bare' ion more reactive towards bond activation. Nevertheless, the oxidative addition of, e.g., a C-H or C-C bond may be precluded by energetic reasons so that the metal ion is either completely unreactive towards the substrate or only gives rise to adduct complexes. One other possibility the metal ion has in this case, is to react by the ion/dipole mechanism [2-61.So far, we found this mechanism to be operative for several alkane derivatives C,H,,+,X; the bare metal ion abstracts the functional group of the substrate as an anion, and this results in the formation of a carbenium-ionidipole complex. Simple separation to afford CnHZn+,+ and neutral MX is in most cases endothermic, however; and thus the complex rearranges by proton transfer from the incipient carbenium ion to the metalcontaining dipole yielding a mixed complex which undergoes competitive ligand loss

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The detailed mechanism for the reaction of bare iron(I) ions with tert-butyl cyanide and isocyanide in the gas phase

Cited by 26 publications

References 2 publications

Collision‐induced dissociation of MCl⁺ adducts (M = Mg, Mn, Zn, Co, Ni and Cu) and Cu⁺ and Ag⁺ adducts of dithioalkyl ketene acetals

Collision‐induced dissociation of MCl⁺ adducts (M = Mg, Mn, Zn, Co, Ni and Cu) and Cu⁺ and Ag⁺ adducts of dithioalkyl ketene acetals

Ion-molecule reaction of alkanenitriles and transition-metal ions in the gas phase: A study on fragmentation mechanism of the adducts

Gas‐Phase Chemistry of Ti⁺ to Zn⁺ with Butyl Isothiocyanate

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The detailed mechanism for the reaction of bare iron(I) ions with tert-butyl cyanide and isocyanide in the gas phase

Cited by 26 publications

References 2 publications

Collision‐induced dissociation of MCl+ adducts (M = Mg, Mn, Zn, Co, Ni and Cu) and Cu+ and Ag+ adducts of dithioalkyl ketene acetals

Collision‐induced dissociation of MCl+ adducts (M = Mg, Mn, Zn, Co, Ni and Cu) and Cu+ and Ag+ adducts of dithioalkyl ketene acetals

Ion-molecule reaction of alkanenitriles and transition-metal ions in the gas phase: A study on fragmentation mechanism of the adducts

Gas‐Phase Chemistry of Ti+ to Zn+ with Butyl Isothiocyanate

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Collision‐induced dissociation of MCl⁺ adducts (M = Mg, Mn, Zn, Co, Ni and Cu) and Cu⁺ and Ag⁺ adducts of dithioalkyl ketene acetals

Collision‐induced dissociation of MCl⁺ adducts (M = Mg, Mn, Zn, Co, Ni and Cu) and Cu⁺ and Ag⁺ adducts of dithioalkyl ketene acetals

Gas‐Phase Chemistry of Ti⁺ to Zn⁺ with Butyl Isothiocyanate