Ab initio study of intramolecular hydrogen transfer in formylperoxy radical

2006 ◽  
Vol 774 (1-3) ◽  
pp. 35-41 ◽  
Author(s):  
Hsiao-Chuan Yang ◽  
Hui-Lung Chen ◽  
Jia-Jen Ho
Keyword(s):  
Ab Initio ◽  
Hydrogen Transfer ◽  
Ab Initio Study ◽  
Intramolecular Hydrogen

scholarly journals A Microwave and Ab Initio Study of the Conformational Properties and Intramolecular Hydrogen Bonding of Cyclopropanemethanethiol.

1991 ◽  
Vol 45 ◽  
pp. 354-360 ◽  
Author(s):  
K.-M. Marstokk ◽  
Harald Møllendal ◽  
Torbjörn Norin ◽  
Ingeborg Csöregh ◽  
Anne Ertan ◽  
...  
Keyword(s):  
Hydrogen Bonding ◽  
Ab Initio ◽  
Intramolecular Hydrogen Bonding ◽  
Ab Initio Study ◽  
Conformational Properties ◽  
Intramolecular Hydrogen

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.

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