scholarly journals Ab Initio Study of Chemical Activation and Hydrogenation of White Phosphorus in Reaction with Rhodium Trihydride Complex

2011 ◽  
Vol 6 (2) ◽  
pp. 84-90
Author(s):  
Iolanta I. Balan ◽  
Natalia N. Gorinchoy
Keyword(s):  
Ab Initio ◽  
Chemical Activation ◽  
White Phosphorus ◽  
Ab Initio Study ◽  
Transient Complex ◽  
Mechanism Of Reaction ◽  
Atom Migration ◽  
The One ◽  
Intramolecular Hydrogen ◽  
Back Donation

The four-stage mechanism of reaction of the rhodium trihydride complex [(triphos)RhH3] (triphos=1,1,1-tris(diphenylphosphanylmethyl)ethane) with the white phosphorus molecule resulting in the phosphane and the cyclo-P3 complex [(triphos)M(η3-P3] is analyzed on the basis of ab initio calculations of reactants, products, and intermediate complexes of reaction. It is shown that generation of the transient complex [(triphos)RhH(η1:η1-P4)] followed by intramolecular hydrogen atom migration from the metal to one of the phosphorus atoms is the energetically favourable process. Calculations also show that P4 molecule is activated by coordination to the above complex: the metal-bonded P-P edge is broken, and the tetrahedron P4 is opened to form the butterfly geometry. This activation is realized mainly due to the one-orbital back donation of 4d-electron density from the atom of Rh to the unoccupied antibonding triple degenerate t1*-MO of P4.

The Structure of N-Acetylprolinamide in the Solid State and in the Gasphase. A Remarkable Lattice Effect as the Result of a Competition Between Inter-and Intramolecular Hydrogen Bonds of Different Strengths

1998 ◽  
Vol 53 (1-2) ◽  
pp. 61-66 ◽  
Author(s):  
Gerhard Raabe ◽  
Axel Sudeikat ◽  
Robert W. Woody
Keyword(s):  
Solid State ◽  
Ab Initio ◽  
Conformational Changes ◽  
Molecular Conformation ◽  
Carbonyl Oxygen ◽  
Basis Set ◽  
Am1 Method ◽  
Lattice Effect ◽  
The One ◽  
Intramolecular Hydrogen

Abstract In the solid state, the conformation of N-actetylprolinamide is stabilized by two intermolecular O···H bridges and one intramolecular N···H hydrogen bond. According to quantum chemical ab initio calculations with the 6-31+G* basis set at the one-determinant level, the intramolecular N ···H bond is not strong enough to maintain the solid-state molecular conformation the gas phase. The conformational changes predominantly consist in a rotation of the amide group about its C-C bond to the proline ring, resulting in a c/s-like conformation which is stabilized by a presumably stronger intramolecular O···H bond between one hydrogen atom of the NH2 group and the carbonyl oxygen of the acetyl subsituent bonded to the nitrogen atom of the five-membered ring. These confirmational changes cause a reduction of the molecular dipole moment by about 50%, indicating that the conformation in solution might be strongly solvent dependent. While both the MINDO/3 and the MNDO method in their standard parametrizations fail to reproduce the ab initio results, the lattice effect is reproduced at least qualitatively with the PM3 as well as with the AM1 method.

Ab initio study of the one-monolayer Sb/Ge interface

2004 ◽  
Vol 566-568 ◽  
pp. 956-960 ◽  
Author(s):  
R. Shaltaf ◽  
M. Çakmak ◽  
E. Mete ◽  
G.P. Srivastava ◽  
Ş. Ellialtıoğlu
Keyword(s):  
Ab Initio ◽  
Ab Initio Study ◽  
The One

Ab initio study of the one-monolayer Sb/Si(001) interface

2003 ◽  
Vol 532-535 ◽  
pp. 661-665 ◽  
Author(s):  
M. Çakmak ◽  
R. Shaltaf ◽  
G.P. Srivastava ◽  
Ş. Ellialtıoǧlu
Keyword(s):  
Ab Initio ◽  
Ab Initio Study ◽  
The One

Platinum-mediated oxidative P–O coupling of white phosphorus and alcohols: an ab initio study

2000 ◽  
Vol 307 (1-2) ◽  
pp. 72-77 ◽  
Author(s):  
Arvydas Tamulis ◽  
Rumiya R. Abdreimova ◽  
Jelena Tamuliene ◽  
Maurizio Peruzzini ◽  
Mindaugas L. Balevicius
Keyword(s):  
Ab Initio ◽  
White Phosphorus ◽  
Ab Initio Study
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