Molecular Structures of Tris(dipivaloylmethanato) Complexes of the Lanthanide Metals, Ln(dpm)3, Studied by Gas Electron Diffraction and Density Functional Theory Calculations:  A Comparison of the Ln−O Bond Distances and Enthalpies in Ln(dpm)3Complexes and the Cubic Sesquioxides, Ln2O3

2006 ◽  
Vol 45 (13) ◽  
pp. 5179-5186 ◽  
Author(s):  
G. V. Girichev ◽  
N. I. Giricheva ◽  
Arne Haaland ◽  
N. P. Kuzmina ◽  
Svein Samdal ◽  
...  
Keyword(s):  
Density Functional Theory ◽  
Electron Diffraction ◽  
Density Functional ◽  
Density Functional Theory Calculations ◽  
Molecular Structures ◽  
Gas Electron Diffraction ◽  
Functional Theory ◽  
Lanthanide Metals

The Molecular Structures and Conformational Preferences of Bis(dimethylstibyl)- Oxane, -Sulfane and -Selane, E(SbMe2)2, E = O, S or Se, Me = CH3, by Density Functional Theory Calculations and Gas Electron Diffraction

1997 ◽  
Vol 52 (2) ◽  
pp. 296-300 ◽  
Author(s):  
Arne Haaland ◽  
Vasili Ivanovitch Sokolov ◽  
Hans Vidar Volden ◽  
Hans Joachim Breunig ◽  
Michael Denker ◽  
...  
Keyword(s):  
Density Functional Theory ◽  
Electron Diffraction ◽  
Density Functional ◽  
Lone Pair ◽  
Density Functional Theory Calculations ◽  
Molecular Structures ◽  
Gas Electron Diffraction ◽  
Electron Diffraction Data ◽  
Functional Theory ◽  
Anti Conformer

Abstract Density Functional Theory calculations on E(SbMe2)2, E = O, S or Se, Me = CH3, indicate that the equilibrium structures are syn-syn or near syn-syn conformers with over-all C2 symmetry. The barriers restricting rotation about E-Sb bonds are very low, the equilibrium values for the dihedral angles ϕ(Sb-E-Sb-lp) where lp denotes the direction of the electron lone pair on one of the Sb atoms are probably less than 45°. The calculations further indicate the existence of syn-anti conformers some 4 kJ mol-1 above the more stable syn-syn. Gas electron diffraction data show that both conformers are present in gaseous O(SbMe2)2, while the presence of the syn-anti conformer in gaseous Se(SbMe2)2 is uncertain; least-squares refinements yielded the mole fraction χ = 0.27(18). The Sb-O and Sb-Se bond distances are 197.6(14) and 255.1(5) pm respectively, the valence angles of the syn-syn conformers are <SbOSb = 122.3(16)° and <SbSeSb = 96.3(11)°. It is suggested that the wide <SbOSb angle is due to across-angle repulsion between the Sb atoms.

The Molecular Structures and Conformational Preferences of Bis(dimethylstibyl)-Sulfane and -Tellurane, E(SbMe2)2, E = S or Te, Me = CH3, by Density Functional Theory Calculations and Gas Electron Diffraction

1998 ◽  
Vol 53 (3) ◽  
pp. 381-385 ◽  
Author(s):  
Arne Haaland ◽  
Dimitry J. Shorokhov ◽  
Hans Vidar Volden ◽  
Hans Joachim Breunig ◽  
Michael Denker ◽  
...  
Keyword(s):  
Density Functional Theory ◽  
Electron Diffraction ◽  
Density Functional ◽  
Density Functional Theory Calculations ◽  
Equilibrium Structure ◽  
Molecular Structures ◽  
Electron Diffraction Data ◽  
Functional Theory ◽  
Anti Conformer ◽  
Equilibrium Structures

Density functional theory calculations on E(SbMe2)2, E = S or Te, Me = CH3, indicate that the equilibrium structures are syn-syn or near syn-syn conformers with overall C2v or C2 symmetry. The calculations further indicate the existence of syn-anti conformers about 4 kJ mol-1 (E = S) or 1 kJ m ol-1 (E = Te) above the equilibrium structure. G as electron diffraction data show that both conform ers are present in gaseous S(SbMe2)2, while the presence of the syn-anti conformer in gaseous Te(SbMe2)2 is uncertain. The Sb - S and Sb - Te bond distances are 241.4(4) and 278.1(3) pm, respectively, the valence angles of the synsyn conformers are <SbSSb = 9 8.7(5)° and <SbTeSb = 91(2)°.

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