scholarly journals Isomerisation of nido-[C2B10H12]2− dianions: unprecedented rearrangements and new structural motifs in carborane cluster chemistry

2015 ◽  
Vol 6 (5) ◽  
pp. 3117-3128 ◽  
Author(s):  
David McKay ◽  
Stuart A. Macgregor ◽  
Alan J. Welch
Keyword(s):  
Dft Calculations ◽  
Structural Motifs ◽  
Cluster Chemistry

The formation and isomerisation of nido-[C2B10H12]2− species is investigated through DFT calculations, which reveal novel basket and inverted nido intermediates and unusual inverconversion pathways, including basket collapse and pivoting triangles and diamonds.

Macropolyhedral Boron-Containing Cluster Chemistry. A Metallathiaborane from S2B17H17: Isolation and Characterisation of [(PMe2Ph)2PtS2B16H16]; A neo-arachno Ten-Vertex Cluster Shape, and the Constitution of the [arachno-B10H15]- Anion

2005 ◽  
Vol 70 (4) ◽  
pp. 430-440 ◽  
Author(s):  
Michael J. Carr ◽  
Michael G. S. Londesborough ◽  
Jonathan Bould ◽  
Ivana Císařová ◽  
Bohumil Štíbr ◽  
...  
Keyword(s):  
Dft Calculations ◽  
Sodium Hydride ◽  
Hydrogen Atoms ◽  
Subsequent Reaction ◽  
Cluster Chemistry ◽  
Cluster Shape ◽  
Open Face

The deprotonation of S2B17H17 with sodium hydride and subsequent reaction with [PtCl2(PMe2Ph)2] gives the new macropolyhedral metallathiaborane [(PMe2Ph)2PtS2B16H16], of which the cluster consists of a conventional eleven-vertex nido {SB10} unit, fused, with two boron atoms in common, with a {PtSB8} unit of unique ten-vertex neo-arachno constitution and geometry. The latter geometry suggests a configuration for the previously structurally uncharacterised [B10H15]- anion; starting from this configuration, DFT calculations of structure and thence of boron nuclear shieldings, which are found very closely to mimic those found experimentally, thence support a fluxional structure for [B10H15]- with three {BHB(bridging)} and two {BH(endo)} hydrogen atoms around a six-membered open face.

Novel nickel–cobalt phosphite with face-sharing octahedra derived electrocatalyst for efficient water splitting

2019 ◽  
Vol 6 (8) ◽  
pp. 2014-2023 ◽  
Author(s):  
Jian Wu ◽  
Lingling Lin ◽  
Francois J. Morvan ◽  
Juan Du ◽  
Weibin Fan
Keyword(s):  
Electronic Structure ◽  
Catalytic Activity ◽  
Dft Calculations ◽  
Water Splitting ◽  
Exchange Effect ◽  
Structural Motifs ◽  
Nickel Cobalt ◽  
Local Electronic Structure

Nickel–cobalt phosphite (CoNiPO) including local structural motifs with face-sharing octahedra shows excellent OER activity. The derivatized electrocatalyst (NiP2@CoNiPO) exhibits high HER activity. DFT calculations indicated the super-exchange effect in CoNiPO can adjust local electronic structure and improve their catalytic activity.

New structural motifs in Mn cluster chemistry from the ketone/gem-diol and bis(gem-diol) forms of 2,6-di-(2-pyridylcarbonyl)pyridine: {MnII4MnIII2} and {MnII4MnIII6} complexes

RSC Advances ◽  
2016 ◽  
Vol 6 (107) ◽  
pp. 105969-105979 ◽  
Author(s):  
Dimosthenis P. Giannopoulos ◽  
Luís Cunha-Silva ◽  
Rafael Ballesteros-Garrido ◽  
Rafael Ballesteros ◽  
Belén Abarca ◽  
...  
Keyword(s):  
Structural Motifs ◽  
Cluster Chemistry ◽  
Mn Cluster

The ketone/gem-diol (L1H2) and bis(gem-diol) (L2H4) forms of the ligand 2,6-di-(2-pyridylcarbonyl)pyridine in Mn cluster chemistry have afforded the new complexes [MnII4MnIII2(N3)6Cl4(L1)2(DMF)4] and [MnII4MnIII6O2(N3)12(L1)2(L2H)2(DMF)6].

Pyrimidine and s-triazine as structural motifs for ordered adsorption on Si(100): a first principles study

2015 ◽  
Vol 17 (26) ◽  
pp. 16876-16885 ◽  
Author(s):  
Wilson K. H. Ng ◽  
J. W. Liu ◽  
Zhi-Feng Liu
Keyword(s):  
Low Temperature ◽  
Dft Calculations ◽  
First Principles ◽  
Structural Motifs ◽  
First Principles Study ◽  
Kinetically Controlled

Kinetically controlled chemisorption of s-triazine on Si(100) at low temperature would produce an ordered zig-zag pattern, according to DFT calculations.

Structure elucidation of a proton-deficient natural product using LR-HSQMBC supported by DFT calculations

Planta Medica ◽  
2015 ◽  
Vol 81 (11) ◽  
Author(s):  
J Saurí ◽  
STS Chan ◽  
AV Buevich ◽  
KR Gustafson ◽  
RT Williamson ◽  
...  
Keyword(s):  
Dft Calculations ◽  
Natural Product ◽  
Structure Elucidation

Reactions of an Aluminium(I) Reagent with 1,2-, 1,3- and 1,5-Dienes: Dearomatisation, Reversibility, and a Pericyclic Mechanism

2019 ◽  
Author(s):  
Clare Bakewell ◽  
Martí Garçon ◽  
Richard Y Kong ◽  
Louisa O'Hare ◽  
Andrew J. P. White ◽  
...  
Keyword(s):  
Reaction Mechanism ◽  
Dft Calculations ◽  
Transition State ◽  
Reaction Pathways ◽  
Aromatic Rings ◽  
Aromatic Character ◽  
Pericyclic Reaction

The reactions of an aluminium(I) reagent with a series of 1,2-, 1,3- and 1,5-dienes are reported. In the case of 1,3-dienes the reaction occurs by a pericyclic reaction mechanism, specifically a cheletropic cycloaddition, to form aluminocyclopentene containing products. This mechanism has been interrogated by stereochemical experiments and DFT calculations. The stereochemical experiments show that the (4+1) cycloaddition follows a suprafacial topology, while calculations support a concerted albeit asynchronous pathway in which the transition state demonstrates aromatic character. Remarkably, the substrate scope of the (4+1) cycloaddition includes dienes that are either in part, or entirely, contained within aromatic rings. In these cases, reactions occur with dearomatisation of the substrate and can be reversible. In the case of 1,2- or 1,5-dienes complementary reactivity is observed; the orthogonal nature of the C=C π-bonds (1,2-diene) and the homoconjugated system (1,5-diene) both disfavour a (4+1) cycloaddition. Rather, reaction pathways are determined by an initial (2+1) cycloaddition to form an aluminocyclopropane intermediate which can in turn undergo insertion of a further C=C π-bond leading to complex organometallic products that incorporate fused hydrocarbon rings.

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