The structural significance of the number of skeletal bonding electron-pairs in carboranes, the higher boranes and borane anions, and various transition-metal carbonyl cluster compounds

Wade, K.

doi:10.1039/c29710000792

Cited by 848 publications

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“…The carboranes are classified into different types depending on the skeletal structural variation, for example, closo, nido, and arachno [124,125]. Oxidation potentials for 31 icosahedral carborane anions [1-X-12-Y-CB 11 Me 10 − ] were calculated at three different levels of theoretical methods, such as the RI-B3LYP, RI-BP86, and RI-HF (RI is the resolution of identity, an algorithm to speed-up HF and DFT calculations).…”

Section: Inorganic Compoundsmentioning

confidence: 99%

Computational Redox Potential Predictions: Applications to Inorganic and Organic Aqueous Complexes, and Complexes Adsorbed to Mineral Surfaces

Arumugam

Becker

2014

Minerals

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Abstract:Applications of redox processes range over a number of scientific fields. This review article summarizes the theory behind the calculation of redox potentials in solution for species such as organic compounds, inorganic complexes, actinides, battery materials, and mineral surface-bound-species. Different computational approaches to predict and determine redox potentials of electron transitions are discussed along with their respective pros and cons for the prediction of redox potentials. Subsequently, recommendations are made for certain necessary computational settings required for accurate calculation of redox potentials. This article reviews the importance of computational parameters, such as basis sets, density functional theory (DFT) functionals, and relativistic approaches and the role that physicochemical processes play on the shift of redox potentials, such as hydration or spin orbit coupling, and will aid in finding suitable combinations of approaches for different chemical and geochemical applications. Identifying cost-effective and credible computational approaches is essential to benchmark redox potential calculations against experiments. Once a good theoretical approach is found to model the chemistry and thermodynamics of the redox and electron transfer process, this knowledge can be incorporated into models of more complex reaction mechanisms that include diffusion in the solute, surface diffusion, and dehydration, to name a few. This knowledge is important to fully understand the nature of redox processes be it a geochemical process that dictates natural redox reactions or one that is being used for the optimization of a chemical process in industry. In addition, it will help identify materials that will be useful to design catalytic OPEN ACCESSMinerals 2014, 4 346 redox agents, to come up with materials to be used for batteries and photovoltaic processes, and to identify new and improved remediation strategies in environmental engineering, for example the reduction of actinides and their subsequent immobilization. Highly under-investigated is the role of redox-active semiconducting mineral surfaces as catalysts for promoting natural redox processes. Such knowledge is crucial to derive process-oriented mechanisms, kinetics, and rate laws for inorganic and organic redox processes in nature. In addition, molecular-level details still need to be explored and understood to plan for safer disposal of hazardous materials. In light of this, we include new research on the effect of iron-sulfide mineral surfaces, such as pyrite and mackinawite, on the redox chemistry of actinyl aqua complexes in aqueous solution.

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Section: Inorganic Compoundsmentioning

confidence: 99%

Computational Redox Potential Predictions: Applications to Inorganic and Organic Aqueous Complexes, and Complexes Adsorbed to Mineral Surfaces

Arumugam

Becker

2014

Minerals

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“…The Wade-Mingos rules (Wade, 1971;Mingos, 1972Mingos, , 1984Mingos, , 1991 have widely been utilized to categorize clusters. The 4n series method of categorizing clusters that has recently been developed (Kiremire, 2015a;2015b) complements the PSEPT method.…”

Section: Introductionmentioning

confidence: 99%

The Application of the 4n Series Method to Categorize Metalloboranes

Kiremire¹

2016

IJC

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Metalloboranes have been categorized by using 4n series method. More than one hundred metalloboranes have been analyzed and characterized by the method. The clusters have been found to be centered within the series range S = 4n+6 to 4n-8. According to the classification, the clusters of series S= 4n+0 are mono-capped, S = 4n-2, bi-capped, S = 4n-4, tri-capped, S = 4n-6, tetra-capped and S= 4n-8, penta-capped. Whereas the known stable boranes have almost non-existent capped boranes, such clusters are prevalent within metalloborane complexes. This implies that metal fragments have the potency of stabilizing the fragile capped boranes.

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“…The Wade-Mingos rules (PSEPT) have been exceedingly helpful in analyzing and categorizing clusters for several decades (Wade, 1971;Mingos, 1972;Rudolph, 1976;Welch, 2013). In an attempt to understand these rules and the pattern within clusters especially the osmium carbonyls, the 14n and 4n rules were revealed for transition and main group elements (Kiremire, 2014;Kiremire, 2015a).…”

Section: Introductionmentioning

confidence: 99%

The Outstanding Applications of Skeletal Numbers to Chemical Clusters

Kiremire¹

2017

IJC

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The evolution of the use of the 14/4n series method has resulted in the discovery of skeletal numbers. The skeletal numbers have rendered the testing of the 18-and 8-electron rules much easier and faster. In the same way, they have been very useful in simplifying the categorization of clusters, the prediction of shapes, and the matching of isolobal fragments. Furthermore, the skeletal numbers have made it possible to tentatively assign ligands to individual skeletal elements in such way that the 18-or 8-electron rule is obeyed. Thus, skeletal numbers can be utilized as a simple guide in analyzing and understanding clusters.

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The structural significance of the number of skeletal bonding electron-pairs in carboranes, the higher boranes and borane anions, and various transition-metal carbonyl cluster compounds

Cited by 848 publications

References 0 publications

Computational Redox Potential Predictions: Applications to Inorganic and Organic Aqueous Complexes, and Complexes Adsorbed to Mineral Surfaces

Computational Redox Potential Predictions: Applications to Inorganic and Organic Aqueous Complexes, and Complexes Adsorbed to Mineral Surfaces

The Application of the 4n Series Method to Categorize Metalloboranes

The Outstanding Applications of Skeletal Numbers to Chemical Clusters

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