Investigation of the basis of the valence shell electron pair repulsion model by ab initio calculation of geometry variations in a series of tetrahedral and related molecules

1979 ◽  
Vol 101 (8) ◽  
pp. 2002-2010 ◽  
Author(s):  
Ann Schmiedekamp ◽  
D. W. J. Cruickshank ◽  
Steen Skaarup ◽  
Peter Pulay ◽  
Istvan Hargittai ◽  
...  
Keyword(s):  
Ab Initio ◽  
Ab Initio Calculation ◽  
Electron Pair ◽  
Valence Shell ◽  
Shell Electron

scholarly journals Valence‐Shell Electron‐Pair Repulsion Theory Revisited: An Explanation for Core Polarization

2019 ◽  
Vol 25 (46) ◽  
pp. 10938-10945 ◽  
Author(s):  
Julen Munárriz ◽  
Mónica Calatayud ◽  
Julia Contreras‐García
Keyword(s):  
Electron Pair ◽  
Valence Shell ◽  
Core Polarization ◽  
Shell Electron

The role of non-bonding electron pairs in the asymmetric coordination environments of 1,1-dithiolate complexes

1976 ◽  
Vol 29 (11) ◽  
pp. 2541 ◽  
Author(s):  
BF Hoskins ◽  
CD Pannan
Keyword(s):  
Electron Pair ◽  
Central Atom ◽  
Main Group ◽  
Valence Shell ◽  
Electron Pairs ◽  
Shell Electron ◽  
Dithiolate Complexes ◽  
Asymmetric Coordination ◽  
Bonding Electron

Various forms of asymmetry in the lengths of the bond between the central atom and sulphur, found in differing coordination environments of 1,1-dithiolate compounds involving main group atoms, have been successfully rationalized by considering both the valence shell electron pair repulsion theory and the effect of the restricted ligand bite distance.

New aspects on the reactivity of MoO2(S2CNEt2)2 with Me3SiX. A peculiar trans effect control

1999 ◽  
Vol 77 (9) ◽  
pp. 1521-1527 ◽  
Author(s):  
H Teruel ◽  
A Sierraalta
Keyword(s):  
Ab Initio ◽  
Ab Initio Calculation ◽  
Valence Shell ◽  
Concentration Region ◽  
Electronic Density ◽  
Trans Effect ◽  
Local Charge ◽  
Free Region ◽  
Charge Concentration ◽  
The Stability

The reaction of MoO2(S2CNEt2)2 with Me3SiI and Me3SiNCS yielded MoOI2(S2CNEt2)2 and MoO(NCS)2(S2CNEt2)2, respectively, similar to results reported for Me3SiCl and Me3SiBr. On the contrary, MoO(OSiMe3)CN(S2CNEt2)2 was the only compound isolated from the reaction of MoO2(S2CNEt2)2 with Me3SiCN. To study the effects of ligands on the reactivity of siloxy compounds, ab initio calculations were undertaken for Mo(OSiH3)L(S2CNH2)2 molecules, for L = Cl, Br, I, NCS, and CN. The electronic density, ρ(r), was analysed by means of the topological theory of Atoms in Molecules (AIM). The analysis of -del2ρ(r) critical points (CPs) at the molybdenum valence shell showed, only in the case of L = CN, a local charge concentration region (N-type CPs) susceptible to electrophilic attacks. However, for L = Cl, Br, I, and NCS, local charge depletion sites (E-type CPs) were found in a bond-free region. The absence of any accessible E-type CPs and the presence of an N-type CP in the same region, opposite to the Mo=O group, justified the stability of Mo(OSiMe3)L(S2CNEt2)2 for L = CN, and the formation of MoOL2(S2CNEt2)2 for L = Cl, Br, I, and NCS by further reaction with the corresponding Me3SiL.Key words: ab initio calculation, electronic density, Mo-siloxy compound, reactivity, theoretical.

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