Unimolecular dissociation kinetics and collision-induced dissociation of dimanganese decacarbonyl(1+): determination of individual bond dissociation energies

Yu, Wangsheng; Liang, Xiangqiu.; Freas, R. B.

doi:10.1021/j100162a032

Cited by 6 publications

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“…In terms of energetics, the facile formation of [Mn(Me 3 TACN)] + in the reactions of the [Mn 2 (CO) 2 ] + ion with the Me 3 TACN ligand indicates that sufficient energy needs to be liberated upon incorporation of the organic ligand for the expulsion of both CO ligands and the cleavage of the MnMn bond for the overall process to be exothermic to thermoneutral. Based on the suggested average value for the CO BDE of the [Mn 2 (CO) 10 ] + ion of 70–75 kJ mol −1 ,32 the loss of the two CO ligands may require about 150 kJ mol −1 , whereas the cleavage of the Mn–Mn bond requires more than about 200 kJ mol −1 according to reported CID experiments concerned with the threshold energy for the loss of Mn from the [Mn 2 (CO) 2 ] + ion 33. This suggests that the BDE of the [Mn(Me 3 TACN)] + complex exceeds 350 kJ mol −1 , in line with the consideration for the reaction of the [Mn(CO) 5 ] + ion ( vide supra ).…”

Section: Discussionmentioning

confidence: 99%

Reactions of (di)manganese carbonyl ions with 1,4,7‐trimethyl‐1,4,7‐triazacyclononane (Me₃TACN) in the gas phase

Beelen

Ingemann

2005

Rapid Comm Mass Spectrometry

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The gas-phase reactions of a series of (di)manganese carbonyl positive ions with 1,4,7-trimethyl-1,4,7-triazacyclononane (Me(3)TACN) have been examined with the aid of Fourier transform ion cyclotron resonance (FTICR) mass spectrometry. The monomanganese carbonyl ions, [Mn(CO)(n)](+) (n = 2-5), react predominantly by ligand exchange and to a minor extent by electron transfer with the formation of the radical cation of Me(3)TACN. For the [Mn(CO)(n)](+) (n = 2-4) ions, the ligand exchange results in the exclusive formation of a [Mn(Me(3)TACN)](+) complex, whereas small amounts of [Mn(CO)(Me(3)TACN)](+) ions are also generated in the reactions of the [Mn(CO)(5)](+) ion. The [Mn(2)(CO)(n)](+) ions (n = 2, 4 and 5) react also by competing electron transfer and ligand exchange. The reaction of the [Mn(2)(CO)(2)](+) and [Mn(2)(CO)(4)](+) ions is associated with cleavage of the Mn--Mn bond as evidenced by the pronounced formation of [Mn(Me(3)TACN)](+) ions. For [Mn(2)(CO)(5)](+), the ligand exchange leads mainly to the formation of [Mn(2)(CO)(n)(Me(3)TACN)](+) (n = 1-3) ions. These primary product ions react subsequently by the incorporation of a second Me(3)TACN molecule to afford [Mn(2)(CO)(Me(3)TACN)(2)](+) and [Mn(2)(CO)(2)(Me(3)TACN)(2)](+) ions. Both of these latter species incorporate an oxygen molecule with formation of ions with the assigned composition of [Mn(2)(O(2))(CO)(Me(3)TACN)(2)](+) and [Mn(2)(O(2))(CO)(2)(Me(3)TACN)(2)](+).

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Section: Discussionmentioning

confidence: 99%

Reactions of (di)manganese carbonyl ions with 1,4,7‐trimethyl‐1,4,7‐triazacyclononane (Me₃TACN) in the gas phase

Beelen

Ingemann

2005

Rapid Comm Mass Spectrometry

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Energetics of Organomanganese Compounds

Liebman

Slayden

2011

Patai's Chemistry of Functional Groups

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Diverse aspects of the energetics of organomanganese compounds are considered in this chapter. Bond energies, enthalpies of formation and enthalpies of reaction are discussed. Classical combustion calorimetry plays only a small role compared to reaction calorimetry and techniques from contemporary ion energetics. While carbonyl, cyano, cyclopentadienyl, and benzene derivatives dominate the discussion, species with numerous other σ and/or π‐bonded ligands also appear. Quantitation is given whenever possible.

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Mass Spectrometry and Gas‐Phase Ion Chemistry of Organomanganese Complexes

Palii

Zagorevskii

2011

Patai's Chemistry of Functional Groups

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This review (782 references) represents an exhaustive up‐to‐date survey of literature on mass spectrometry and gas‐phase ion chemistry of organomanganese complexes. Fundamental physico‐chemical characteristics of organomanganese ionic species, as well as the gas‐phase reactions resulting in the dissociation or formation of manganese‐carbon bond(s) are examined. Circa 300 examples of ion/molecule reactions characterizing the reactivity of Mn + , positively or negatively charged manganese clusters, as well as neutrals, cations and anions of various Mn‐containing species (including coordinatively unsaturated ones) are summarized. A variety of studies involving tandem mass spectrometry, neutralization‐reionization mass spectrometry, collision‐induced dissociation, multiple‐photon dissociation, IRMPD spectroscopy and theoretical calculations for organomanganese ion structure characterization are discussed. Additionally, analytical applications of mass spectrometric techniques to the characterization of compounds containing a MnC bond are reviewed. These include a number of relatively simple mononuclear complexes, polynuclear clusters, complexes incorporating organometallic units bridged with organic fragment(s), bifunctional compounds containing organometallic and classical Werner‐type coordination sites, fullerenes or planar polyaromatic hydrocarbons with an organomanganese fragment attached to them, manganospiralenes, manganoscorpionates, supramolecular entities, cymantrene‐peptide bioconjugates, etc.

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Unimolecular dissociation kinetics and collision-induced dissociation of dimanganese decacarbonyl(1+): determination of individual bond dissociation energies

Cited by 6 publications

References 0 publications

Reactions of (di)manganese carbonyl ions with 1,4,7‐trimethyl‐1,4,7‐triazacyclononane (Me₃TACN) in the gas phase

Reactions of (di)manganese carbonyl ions with 1,4,7‐trimethyl‐1,4,7‐triazacyclononane (Me₃TACN) in the gas phase

Energetics of Organomanganese Compounds

Mass Spectrometry and Gas‐Phase Ion Chemistry of Organomanganese Complexes

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Unimolecular dissociation kinetics and collision-induced dissociation of dimanganese decacarbonyl(1+): determination of individual bond dissociation energies

Cited by 6 publications

References 0 publications

Reactions of (di)manganese carbonyl ions with 1,4,7‐trimethyl‐1,4,7‐triazacyclononane (Me3TACN) in the gas phase

Reactions of (di)manganese carbonyl ions with 1,4,7‐trimethyl‐1,4,7‐triazacyclononane (Me3TACN) in the gas phase

Energetics of Organomanganese Compounds

Mass Spectrometry and Gas‐Phase Ion Chemistry of Organomanganese Complexes

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Product

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Reactions of (di)manganese carbonyl ions with 1,4,7‐trimethyl‐1,4,7‐triazacyclononane (Me₃TACN) in the gas phase

Reactions of (di)manganese carbonyl ions with 1,4,7‐trimethyl‐1,4,7‐triazacyclononane (Me₃TACN) in the gas phase