The VSEPR model revisited

Gillespie, R. J.

doi:10.1039/cs9922100059

Cited by 212 publications

(130 citation statements)

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“…Regions where charge is concentrated, which are revealed by the Laplacian of the charge density (~' p ) (8)(9)(10) have played an important role in understanding the VSEPR model, resulting in it being reformulated in terms of electron-pair domains (2,3,11,12) i.e., the regions in the valence shell where charge is locally concentrated.…”

Section: Introductionmentioning

confidence: 99%

“…Perhaps the simplest set of rules that can be used to understand and classify molecular geometries are those of the valence shell electron pair repulsion (VSEPR) model (1)(2)(3). The VSEPR model requires that we consider the strength of mutual repulsions between the different types of electron pairs present within the molecule in order to obtain its preferred, or energetically most favourable, geometry.…”

Section: Introductionmentioning

confidence: 99%

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Topological studies of the charge density of some group 2 metallocenes M(η⁵-C₅H₅)₂ (M = Mg or Ca)

Bytheway¹,

Popelier²,

Gillespie³

1996

Can. J. Chem.

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Ab initio quantum chemical calculations using both the Hartree-Fock and the B3LYP density functional theory methods have been performed for the group 2 metallocenes M(~~-c,H,), (M = Mg or Ca). The topology of the calculated charge density (p) and its Laplacian (vZp) have been analysed using a new critical point search algorithm in order to understand whyis linear while C~(~~-C , H , ) , is bent. The Laplacian of the core of the Ca atom in c~(~~-c , H , )~ is perturbed by the polarizing field of the cyclopentadienyl ligands and the bent geometry is a consequence of the interactions between the distorted core and the ligand atoms. In the case of M~ (~~-c , H , ) , , charge concentration maxima in the Mg core occur along the vectors connecting the metal to the centroids of the cyclopentadienyl ligands irrespective of whether or not the molecule is linear, and the preferred geometry is linear as expected. The results of these calculations demonstrate that the geometries of the group 2 metallocenes can be understood in terms of the repulsive interactions between the ligands and between the ligands and the distorted core of the metal atom.

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Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Topological studies of the charge density of some group 2 metallocenes M(η⁵-C₅H₅)₂ (M = Mg or Ca)

Bytheway¹,

Popelier²,

Gillespie³

1996

Can. J. Chem.

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“…It should be noted that the increase of bond lengths compared to not deformed octahedron in this case is 0.27Å, whereas the decrease in length of the opposite bonds is 0.20Å. The changes in geometry are the result of the change of the position of the lone electron pair, in comparison to a situation without a deformation of the octahedral coordination [12,13].…”

Section: Introductionmentioning

confidence: 98%

“…As at 340 K, at 260 K there is observed a so-called transinfluence, which consists of a shortening of the Sb-Cl bonds placed opposite to those which are elongated by N-H...Cl hydrogen bonds. The influence is mainly related to the stereochemical activity of the electron lone pair located on the Sb atom [12,13].…”

Section: Structure At 260 Kmentioning

confidence: 99%

Phase Transitions Mechanism and Distortion of SbCl₆ ³– Octahedra in Bis(n-butylammonium) Pentachloroantimonate(III) (C₄H₉NH₃)₂[SbCl₅]

Zarychta

Zaleski

2006

Zeitschrift Für Naturforschung B

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Bis(n-butylammonium) pentachloroantimonate(III) was obtained in a reaction of n-butylammonium chloride and antimony trichloride (molar ratio 2 : 1; cation : Sb) in acidic aqueous solution. To obtain further information about the mechanism of the earlier reported phase transitions at 229 and 315 K the structure was determined at 100, 260 and 340 K. The orthorhombic system was found in all phases, space groups Ibam at 340 K and Pccn at 260 and 100 K. In all phases the anionic sublattice consists of [SbCl 6 ] 3− octahedra, connected via cis chlorine atoms, forming onedimensional zig-zag {[SbCl 5 ] 2− } n chains extended along the c direction. The n-butylammonium cations are located between the inorganic chains, with -NH 3 + groups facing the oppositely charged polyanions. The phase transitions are of the order-disorder type. They are related to changes in molecular dynamics of the n-butylammonium cations. At high temperature the cations reorient, on decreasing temperature the reorientations are successfully frozen. This leads to the formation on N-H...Cl hydrogen bonds, which significantly deform the octahedral coordination of the Sb atoms.

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“…There is, in principle a one-to-one correspondence between the VSEPR electronic domains and the valence basins of the ELF function. Indeed, the VSEPR model relies on a distribution of the valence electron pairs among bonding and nonbonding electron domains, [55] which are defined as the region of space in which the probability of finding an (opposite spin) electron pair is high. In the ELF analysis, the valence basins are characterized by the number of atomic valence shells in which they participate.…”

Section: Computational Methodologiesmentioning

confidence: 99%

What governs nitrogen configuration in substituted aminophosphines?

Wodrich

Vargas

Morgantini

et al. 2008

J of Physical Organic Chem

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The trigonal planar geometry of the nitrogen atom in commonly used phosphoramidite ligands is not in line with the traditional valence shell electron pair repulsion (VSEPR) model. In this work, the effects governing nitrogen configuration in several substituted aminophosphines, A 2 PNB 2 (A or B ¼ H, F, Cl, Br, Me, OMe, BINOP), are examined using modern computational analytic tools. The electron delocalization descriptions provided by both electron localization function (ELF) and block localized wavefunction analysis support the proposed relationships between conformation and negative hyperconjugative interactions. In the parent H 2 PNH 2 , the pyramidal nitrogen configuration results from nitrogen lone pair electron donation into the s * P-H orbital. While enhanced effects are seen for F 2 PNMe 2 , placing highly electronegative fluorine substituents on nitrogen (i.e., Me 2 PNF 2 ) eliminates delocalization of the nitrogen lone pair. Understanding and quantifying these effects can lead to greater flexibility in designing new catalysts.

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The VSEPR model revisited

Cited by 212 publications

References 15 publications

Topological studies of the charge density of some group 2 metallocenes M(η⁵-C₅H₅)₂ (M = Mg or Ca)

Topological studies of the charge density of some group 2 metallocenes M(η⁵-C₅H₅)₂ (M = Mg or Ca)

Phase Transitions Mechanism and Distortion of SbCl₆ ³– Octahedra in Bis(n-butylammonium) Pentachloroantimonate(III) (C₄H₉NH₃)₂[SbCl₅]

What governs nitrogen configuration in substituted aminophosphines?

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The VSEPR model revisited

Cited by 212 publications

References 15 publications

Topological studies of the charge density of some group 2 metallocenes M(η5-C5H5)2 (M = Mg or Ca)

Topological studies of the charge density of some group 2 metallocenes M(η5-C5H5)2 (M = Mg or Ca)

Phase Transitions Mechanism and Distortion of SbCl6 3– Octahedra in Bis(n-butylammonium) Pentachloroantimonate(III) (C4H9NH3)2[SbCl5]

What governs nitrogen configuration in substituted aminophosphines?

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Topological studies of the charge density of some group 2 metallocenes M(η⁵-C₅H₅)₂ (M = Mg or Ca)

Topological studies of the charge density of some group 2 metallocenes M(η⁵-C₅H₅)₂ (M = Mg or Ca)

Phase Transitions Mechanism and Distortion of SbCl₆ ³– Octahedra in Bis(n-butylammonium) Pentachloroantimonate(III) (C₄H₉NH₃)₂[SbCl₅]