Fragmentation of Transition Metal Carbonyl Cluster Anions: Structural Insights from Mass Spectrometry

Butcher, Colin P. G.; Dyson, Paul J.; Johnson, Brian F. G.; Khimyak, Tetyana; McIndoe, J. Scott

doi:10.1002/chem.200390116

Cited by 30 publications

(24 citation statements)

References 81 publications

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“…The corresponding cluster k values of the fragment should be on the increase. Very interesting extensive work on the metal carbonyls that involves stripping off the CO ligands has been done by several research groups (Butcher, et al, 2002(Butcher, et al, , 2003Crawford, et al, 2006;Critchley, et al, 1999;Dyson, et al, 2001;Henderson, et al, 1998Henderson, et al, , 2009 Table 7). Although the series and the skeletal numbers predict that each of the Re skeletal atoms except one should have a hydrogen atom, the structural determination indicates all the hydrogen atoms are bridging (Miessler, et al, 2014) as observed in borane clusters.…”

Section: Limits Of the Carbonyl Cluster Seriesmentioning

confidence: 99%

“…These opposing processes are reflected in Tables 7 and 8. The removal of CO ligands from transition metal carbonyl clusters has been an intense field of research (Critchley, et al, 1999, Douglas, et al, 2001, Butcher, et al, 2002, 2003, Crawford, et al, 2006, Henderson, et al, 2009). The silicon clusters Si n (n=4-10) were theoretically studied (Slee, et al, 1989) (Hughes, et al, 2000).…”

Section: Capping and De-capping Seriesmentioning

confidence: 99%

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A Hypothetical Model for the Formation of Transition Metal Carbonyl Clusters Based upon 4n Series Skeletal Numbers

Kiremire¹

2016

IJC

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Skeletal numbers of elements have been introduced as derivatives of the 4n series method. They are based on the number of valence electrons present in the skeletal element. They are extremely useful in deducing possible shapes of skeletal elements in molecules or clusters especially the small to medium ones. For large skeletal clusters, the skeletal numbers may simply be regarded as identity numbers. In carbonyl clusters, they can be used as a guide to facilitate the distribution of the ligands such as CO, H and charges onto the skeletal atoms. A naked skeletal cluster may be viewed as a reservoir for skeletal linkages which get utilized when ligands or electrons get bound to it. The sum of linkages used up by the ligands bound to a skeletal fragment and the remaining cluster skeletal numbers is equal to the number of the skeletal linkages present in the original "naked parent" skeletal cluster. The skeletal numbers can be used as a quick way of testing whether or not a skeletal atom obeys the 8-or 18-electron rules.

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Section: Limits Of the Carbonyl Cluster Seriesmentioning

confidence: 99%

Section: Capping and De-capping Seriesmentioning

confidence: 99%

A Hypothetical Model for the Formation of Transition Metal Carbonyl Clusters Based upon 4n Series Skeletal Numbers

Kiremire¹

2016

IJC

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“…An illustration is given in Table 6. Butcher, et al, 2003 DIFFERENCES BETWEEN THE 4n SERIES METHOD AND THE SEP METHOD…”

Section: Blackholes In the Nucleus And Ghost Skeletal Elementsmentioning

confidence: 99%

“…The analysis and categorization of stripping series of clusters may assist in improvement of understanding and appreciation of the work by Butcher and his research groups (Butcher, et al, 2003).…”

Section:  the Stripping Series Of Clustersmentioning

confidence: 99%

Graph Theory of Chemical Series and Broad Categorization of Clusters

Kiremire¹

2018

IJC

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The recent introduction of skeletal numbers has made it much easier to analyze and categorize a wide range of many chemical clusters. In the process, it has been found that a large number of transition metal clusters with and without ligands are capped and do possess closo nuclear clusters. On the basis of the nuclear index, the clusters have been categorized into groups. The categorization of the clusters will greatly assist in promoting deeper understanding and the synthesis of novel clusters and their applications. A simple concept of graph theory of capping clusters has been introduced.

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“…Transition-metal carbonyl cluster anions provide excellent electrospray ionization mass spectra (ESI-MS), and collision-induced dissociation (CID) can be used to selectively remove some or all of the CO ligands from the metal core [25]. We have used these properties in the past to study the reactivity of [CoRu 3 ]…”

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confidence: 99%

Gas-phase reactivity of ruthenium carbonyl cluster anions

Henderson

Kwok

McIndoe

2008

J. Am. Soc. Mass Spectrom.

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Partially-ligated anionic ruthenium carbonyl clusters react with alkenes, arenes, and alkanes in the gas phase; the products undergo extensive C-H activation and lose dihydrogen and carbon monoxide under collision-induced dissociation conditions. Triethylsilane and phenylsilane are also reactive towards the unsaturated clusters, and oxygen was shown to rapidly break down the cluster core by oxidative cleavage of the metal-metal bonds. These qualitative gas-phase reactivity studies were conducted using an easily-installed and inexpensive modification of a commercial electrospray ionization mass spectrometer. Interpretation of the large amounts of data generated in these studies is made relatively straightforward by employing energydependent electrospray ionization mass spectrometry (EDESI-MS). here are many examples of reactions between molecules and metal cluster ions in the gas phase, and the area has been well reviewed [1,2]. Of intense current interest are those systems in which catalytic reactions (homogeneous or heterogeneous) are modeled [3,4]. The information gleaned from these studies is particularly advantageous in systems where little or nothing is known about reactivity. Interest in the area stems from the fact that the chemistry of highly reactive, metallic nanoparticles is fundamentally difficult to study, and it is high surface area metals and metal oxides that are responsible for the most industrially important heterogeneous catalytic reactions. Any means of gaining insight into the mechanism of these reactions may prove useful in designing more efficient and more selective catalysts. The absence of surfaces, solvents, and counterions make the gas phase a considerably less complicated environment than that found in solution. Just how good the correspondence is between gas-phase and solution results is subject to active debate [5][6][7], but there is little argument that the gas phase benefits from the reduction in the number of variables, especially when dealing with complicated systems. The gas-phase reactivity of a wide variety of partially ligated clusters have been studied, including oxides [8 -11] [18]. and even some mixed species [19,20]. However, for the most part, the extent of ligation is low and, correspondingly, so is the relevance to solution chemistry. Homogeneous catalysis is generally performed under conditions that are relatively mild and in which the catalysts maintain a (near) complete coordination sphere, so the comparison with nearly naked gas-phase metal clusters is somewhat tenuous (though interestingly, may more closely approximate the conditions of heterogeneous catalysis, which frequently involves unligated metal particles on a surface) [21,22].Some work has also been done on partially ligated carbonyl clusters; an early paper by Ridge [23] example by Ridge demonstrated that in a Fourier transform ion cyclotron resonance mass spectrometer (FTICR-MS), partially ligated cationic transition-metal carbonyl clusters generated by electron ionization reacted readily with cycl...

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Fragmentation of Transition Metal Carbonyl Cluster Anions: Structural Insights from Mass Spectrometry

Cited by 30 publications

References 81 publications

A Hypothetical Model for the Formation of Transition Metal Carbonyl Clusters Based upon 4n Series Skeletal Numbers

A Hypothetical Model for the Formation of Transition Metal Carbonyl Clusters Based upon 4n Series Skeletal Numbers

Graph Theory of Chemical Series and Broad Categorization of Clusters

Gas-phase reactivity of ruthenium carbonyl cluster anions

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