Transition-metal cluster ions in the gas phase.  Oxide chemistry of dimeric and trimeric clusters containing iron and cobalt

Jacobson, D. B.; Freiser, Ben S.

doi:10.1021/ja00261a006

Cited by 64 publications

(57 citation statements)

References 2 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…The reactions of cobalt cluster anions with O 2 , CO, and N 2 gases show enormous differences, both in reaction efficiencies and product formation channels. Oxygen reacts rapidly via "etching" type processes to form CoO 2 -and other oxygen-rich oxide anions, in contrast with the reactions of cobalt cluster cations [18][19][20] that yield cobalt-rich oxide cations. Nitrogen is largely inert with the small cobalt cluster anions, very slowing adding a single nitrogen molecule only to the largest sizes studied (n ) 7-8), in dramatic contrast with neutral 6,15-17 and cationic 12,15 cobalt clusters for which nitrogen addition is readily observed.…”

Section: Discussionmentioning

confidence: 99%

Reactions of Cobalt Cluster Anions with Oxygen, Nitrogen, and Carbon Monoxide

Kapiloff

Ervin

1997

J. Phys. Chem. A

View full text Add to dashboard Cite

The chemical reactivity of cobalt cluster anions, Co n -(n ) 2-8), toward O 2 , N 2 , and CO is investigated by flow tube reactor kinetics. The reactivity is highest for the reactions with O 2 and intermediate for CO, while the clusters are nearly inert toward N 2 . Only the largest clusters studied, Co 7 -and Co 8 -, show any evidence for reaction with nitrogen by addition of N 2 at very slow rates. Reactions with O 2 have rapid rate coefficients that are largely independent of cluster size and lead to extensive fragmentation of the clusters. The rate coefficients with CO increase with increasing cluster size. Sequential addition of CO to the cobalt cluster anions leads to the saturated species: Co 2 (CO) 7 -, Co 3 (CO) 10 -, Co 4 (CO) 12 -, Co 5 (CO) 13 -, and Co 6 (CO) 15 -. Skeletal structures are proposed for these saturated clusters in accordance with electron-counting rules.

show abstract

Section: Discussionmentioning

confidence: 99%

Reactions of Cobalt Cluster Anions with Oxygen, Nitrogen, and Carbon Monoxide

Kapiloff

Ervin

1997

J. Phys. Chem. A

View full text Add to dashboard Cite

show abstract

“…The experimental finding that only one NH ligand exchanges with a bridging 0 atom and leads to molecule 4 is not yet understood. The inert behaviour of Fe,O: (2) may be due to 1 2 3 4…”

Section: Secondary Reactions Of Feo: Ions (Xmentioning

confidence: 99%

O‐Atom Transfer to Fe⁺_n Clusters (n = 2–10) from O₂, N₂O and CO₂: “Microoxides of Iron”

Gehret

Irion

1996

Chemistry A European J

View full text Add to dashboard Cite

We report on the gas phase reactions of small Fe clusters (n = 2-10) with O , N O and CO in an FT-ICR mass spectrometer. Under our experimental conditions, clusters of all sizes reacted readily with O and all but the dimer reacted with N O. Only the smallest Fe clusters (n = 2-4) appeared to activate CO . For all X-O molecules (X = O, N , CO), reaction pathways were observed that include the transfer of O atoms. In addition, the reactions with O and N O were accompanied by the loss of one or two Fe atoms. Thermochemical considerations based upon the well-known X-O bond energies were used to calculate Fe -O bond dissociation energies (BDEs) for sizes n = 2-6; these amount to roughly 550 kJ mol and thus are considerably higher than the BDE of the Fe-O ion. All oxidation reactions of the Fe clusters (n = 2-6) studied in more detail were terminated by products of Fe O stoichiometry (x = 1-4). These "microoxides of iron" are not able to activate any further X-O bonds. Secondary reactions of Fe O clusters with C H , C H and NH were investigated for two selected sizes (x = 2, 3) and compared with reactions of the naked Fe clusters.

show abstract

“…, an Fe 2 ? -O bond energy exceeding [346] 498 kJ mol -1 and a photodetachment energy for Fe 2 O - [347] of 151 kJ mol -1 corresponding to ionization from an octet (7 unpaired electrons) to the related septet. Neutral Fe 2 O has not been isolated as a solid.…”

Section: Issuementioning

confidence: 98%

“…In this last anion there is a Fe-O-Fe core. We will not concern ourselves with this species, per se, but rather with the triatomic species Fe 2 O as a gaseous neutral, cation, or anion as studied by gas phase ion chemists who suggested upper bound [346] of 1075 ± 29 kJ mol -1 for the enthalpy of formation of Fe 2 O ? , an Fe 2 ?…”

Section: Issuementioning

confidence: 99%

Interplay of thermochemistry and Structural Chemistry, the journal (volume 18, 2007) and the discipline

Ponikvar

Liebman

2008

Struct Chem

View full text Add to dashboard Cite

In this study, we relate the contents of the journal Structural Chemistry for the calendar year 2007 and thermochemistry. The year's articles were briefly summarized and a thermochemical comment written to supplement them. Frequently questions were asked and future research was suggested.Keywords Structural Chemistry Á Thermochemistry Á Thermodynamics Á Enthalpy of formation Á Enthalpy of phase change Á Enthalpy of reaction As practiced disciplines, structural chemistry and thermochemistry are very often unrelated. In this study, these disciplines are linked as relations are explicitly made using the contents of the journal Structural Chemistry (Vol. 18) for the calendar year 2007 as a scaffold for our analysis, for our selected articles in the discipline of structural chemistry. These studies have been reviewed by us, where we give them a thermochemical flavor. While this commentary is most generally written in terms of brief summaries of literature papers involving enthalpies of formation and/or reaction, not uncommonly we raise questions and even suggest possible future research. We are not, however, going to give a thermochemical slant on book reviews, honorary dedications, and obituaries although these works will be cited in our text.As such, this article is a sequel to our earlier related reviews of Structural Chemistry for the calendar years 2000 through 2004 [1-5]. Reviews for 2005 and 2006 are currently being prepared. Issue 1In the first article in the first issue of Structural Chemistry for 2007, Hargittai [6] asserted that while research is currently usually carried out in big groups, the most important ideas, observations and discoveries still belong to individuals who have to bring down dogmas or open entirely new areas in science. This may bring solace to the thermochemical community in which research groups are generally small, and the number of new practitioners sadly few.In the past decade, the crystal engineering of multidimensional arrays and networks containing metal ions has achieved considerable progress because of the increased interest in the potential utility of these compounds as zeolite-like materials [7-11], catalysts [12], or magnetic materials [13][14][15]. The thermochemistry of these species is complicated by their inherent complexity: however, estimation approaches of their key thermochemical quantities are increasingly reliable [16]. In the second article of this issue, by Wang et al. [17], the versatility of malonate dianion as a ligand for the construction of extended networks with different topologies dependent on the coordination geometry of the metal ion was discussed. The synthesis and structure of a novel malonate-bridged copper(II) compound in which copper(II) ions have two different coordination environments in a novel three-dimensional (3D) network was described. Metal malonates have been studied from a

show abstract

Transition-metal cluster ions in the gas phase. Oxide chemistry of dimeric and trimeric clusters containing iron and cobalt

Cited by 64 publications

References 2 publications

Reactions of Cobalt Cluster Anions with Oxygen, Nitrogen, and Carbon Monoxide

Reactions of Cobalt Cluster Anions with Oxygen, Nitrogen, and Carbon Monoxide

O‐Atom Transfer to Fe⁺_n Clusters (n = 2–10) from O₂, N₂O and CO₂: “Microoxides of Iron”

Interplay of thermochemistry and Structural Chemistry, the journal (volume 18, 2007) and the discipline

Contact Info

Product

Resources

About

Transition-metal cluster ions in the gas phase. Oxide chemistry of dimeric and trimeric clusters containing iron and cobalt

Cited by 64 publications

References 2 publications

Reactions of Cobalt Cluster Anions with Oxygen, Nitrogen, and Carbon Monoxide

Reactions of Cobalt Cluster Anions with Oxygen, Nitrogen, and Carbon Monoxide

O‐Atom Transfer to Fe+n Clusters (n = 2–10) from O2, N2O and CO2: “Microoxides of Iron”

Interplay of thermochemistry and Structural Chemistry, the journal (volume 18, 2007) and the discipline

Contact Info

Product

Resources

About

O‐Atom Transfer to Fe⁺_n Clusters (n = 2–10) from O₂, N₂O and CO₂: “Microoxides of Iron”