Organometallic chemistry in the gas phase

Eller, Karsten; Schwarz, Helmut

doi:10.1021/cr00006a002

Cited by 850 publications

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“…Such metal complex ions have been the subject of extensive study including CID [29 -33] and ion/molecule reactions [34 -36]. These studies have clearly shown the importance of coordination geometry and ligand identity on the reactivities of these ions and are consistent with the much larger body of work devoted to the chemistry of gaseous transition-metal ions [37][38][39][40][41][42][43]. They strongly suggest that a degree of control over ion/ion reactivity might be afforded by selection of metal, metal oxidation state, ligand, and ligand number.…”

mentioning

confidence: 70%

Gas-phase ion/ion reactions of transition metal complex cations with multiply charged oligodeoxynucleotide anions

Barlow

Hodges

Xia

et al. 2008

J. Am. Soc. Mass Spectrom.

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Multiply deprotonated hexadeoxyadenylate anions, (A 6 ϪnH) nϪ , where n ϭ 3-5, have been subjected to reaction with a range of divalent transition-metal complex cations in the gas phase. The cations studied included the bis-and tris-1,10-phenanthroline complexes of Cu II , Fe II , and Co II , as well as the tris-1,10-phenanthroline complex of Ru II . In addition, the hexadeoxyadenylate anions were subjected to reaction with the singly charged Fe III and Co III N,N=-ethylenebis(salicylideneiminato) complexes. The major competing reaction channels are electron-transfer from the oligodeoxynucleotide anion to the cation, the formation of a complex between the anion and cation, and the incorporation of the transition-metal into the oligodeoxynucleotide. The latter process proceeds via the anion/cation complex and involves displacement of the ligand(s) in the transition-metal complex by the oligodeoxynucleotide. Competition between the various reaction channels is governed by the identity of the transition-metal cation, the coordination environment of the metal complex, and the oligodeoxynucleotide charge state. In the case of the divalent metal phenanthroline complexes, competition between electron-transfer and metal ion incorporation is particularly sensitive to the coordination number of the reagent metal complexes. Both electron-transfer and metal ion incorporation occur to significant extents with the bis-phenanthroline ions, whereas the trisphenanthroline ions react predominantly by metal ion incorporation. To our knowledge this work reports the first observations of the gas-phase incorporation of multivalent transition-metal cations into oligodeoxynucleotide anions and represents a means for the selective incorporation of transition-metal counter-ions into gaseous oligodeoxynucleotides. [6 -8] have allowed the formation of gas-phase ions of biopolymers, including oligodeoxynucleotides (ODNs), making these ions amenable to study by mass spectrometry. Like peptides and proteins, ODNs are amphoteric, [9] allowing formation of either positively or negatively charged ions. Formation of negatively charged oligonucleotides is quite facile using ESI and, as a result, negatively charged ODN ions have been the most widely studied [9]. Oligodeoxynucleotide ions with bound metals formed by MALDI or ESI, especially those containing transition metals, have shown fragmentation behavior, which is distinct and complementary to that of ions devoid of metals [6 -8].The study of the interaction of transition metals with DNA is of critical importance, given the variety of roles such interactions fulfill. Transition-metal complexes display nuclease activity and consequently complexes such as (methidium-propyl-EDTA)iron(II) have been utilized as footprinting agents [10]. Ruthenium(II) complexes have been extensively examined as spectroscopic probes of local DNA structure [11,12]. The mechanism of action of the chemotherapeutic agent cisplatin involves binding to DNA to prevent replication [13][14][15]. Mass spectrometry has been u...

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mentioning

confidence: 70%

Gas-phase ion/ion reactions of transition metal complex cations with multiply charged oligodeoxynucleotide anions

Barlow

Hodges

Xia

et al. 2008

J. Am. Soc. Mass Spectrom.

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“…Dehydrogenation by the CpCo ⅐ϩ ion has been classified an oxidative addition/reductive elimination reaction for small alkane systems [16,21]. A similar type reaction likely occurs for the alkanes studied here.…”

Section: Single and Double Dehydrogenationmentioning

confidence: 64%

“…It is thought that the CpCo ⅐ϩ ion preferentially attacks the C™H bond in the initial oxidative addition step due to the strong s character of metal-ligand antibonding orbital, i.e., LUMO (lowest unoccupied molecular orbital) [21]. It is interesting that the CpCo ⅐ϩ ion reacts with n-alkanes exclusively by dehydrogenation, while the Co ϩ ion reacts by dehydrogenation and dealkylation [15][16][17]31]. It has been demonstrated by deuterium labeling, collision-activated dissociation, and ion-molecule studies that the apparent dehydrogenation reaction between Co ϩ and n-butane goes by way of a C™C bond insertion [17,31].…”

Section: Single and Double Dehydrogenationmentioning

confidence: 99%

“…Gas-phase studies have shown that many first-row transition metal ions react with various linear and cyclic saturated aliphatic hydrocarbons [13][14][15][16][17]. Fe ϩ , Co ϩ , and Ni ϩ react efficiently with low molecular mass alkanes (C n H 2nϩ2 , n Ͻ 8) by dehydrogenation (Reactions 1 and 2) and dealkylation (Reaction 3) [16].…”

mentioning

confidence: 99%

“…Fe ϩ , Co ϩ , and Ni ϩ react efficiently with low molecular mass alkanes (C n H 2nϩ2 , n Ͻ 8) by dehydrogenation (Reactions 1 and 2) and dealkylation (Reaction 3) [16].…”

mentioning

confidence: 99%

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Molecular mass determination of saturated hydrocarbons: reactivity of η⁵-cyclopentadienylcobalt ion (CpCo^·+) and linear alkanes up to C-30

Byrd

Guttman

Ridge

2003

J. Am. Soc. Mass Spectrom.

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The present study demonstrates the feasibility of the 5 -cyclopentadienylcobalt ion (CpCo ⅐ϩ ) as a suitable cationization reagent for saturated hydrocarbon analysis by mass spectrometry. Ion/molecule reactions of CpCo ⅐ϩ and three medium chain-length n-alkanes were examined using Fourier-transform ion cyclotron resonance mass spectrometry. Second-order rate constants and reaction efficiencies were determined for the reactions studied. Loss of two hydrogen molecules from the CpCo-alkane ion complex was found to dominate all reactions (Ն80%). Furthermore, this dehydrogenation reaction efficiency increases with increasing chain length. These preliminary results suggest that the CpCo ⅐ϩ ion may be a promising cationization reagent of longer chain saturated hydrocarbons and polyolefins.

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Understanding reactivity with Kohn-Sham molecular orbital theory: E2-SN2 mechanistic spectrum and other concepts

1999

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Organometallic chemistry in the gas phase

Cited by 850 publications

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Gas-phase ion/ion reactions of transition metal complex cations with multiply charged oligodeoxynucleotide anions

Gas-phase ion/ion reactions of transition metal complex cations with multiply charged oligodeoxynucleotide anions

Molecular mass determination of saturated hydrocarbons: reactivity of η⁵-cyclopentadienylcobalt ion (CpCo^·+) and linear alkanes up to C-30

Understanding reactivity with Kohn-Sham molecular orbital theory: E2-SN2 mechanistic spectrum and other concepts

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Organometallic chemistry in the gas phase

Cited by 850 publications

References 0 publications

Gas-phase ion/ion reactions of transition metal complex cations with multiply charged oligodeoxynucleotide anions

Gas-phase ion/ion reactions of transition metal complex cations with multiply charged oligodeoxynucleotide anions

Molecular mass determination of saturated hydrocarbons: reactivity of η5-cyclopentadienylcobalt ion (CpCo·+) and linear alkanes up to C-30

Understanding reactivity with Kohn-Sham molecular orbital theory: E2-SN2 mechanistic spectrum and other concepts

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Molecular mass determination of saturated hydrocarbons: reactivity of η⁵-cyclopentadienylcobalt ion (CpCo^·+) and linear alkanes up to C-30