Theoretical studies of inorganic and organometallic reaction mechanisms. 3. The origin of the difference in the barrier for the kinetic and thermodynamic products for the oxidative addition of dihydrogen to a square-planar iridium complex

1992 ◽  
Vol 114 (2) ◽  
pp. 517-522 ◽  
Author(s):  
Andrew L. Sargent ◽  
Michael B. Hall ◽  
Martyn F. Guest
Keyword(s):  
Reaction Mechanisms ◽  
Oxidative Addition ◽  
Iridium Complex ◽  
Theoretical Studies ◽  
Square Planar ◽  
The Difference

Activation entropy as a dominant factor in the oxidative addition of some group IV hydrides to an iridium(I) complex

1976 ◽  
Vol 54 (19) ◽  
pp. 3102-3109 ◽  
Author(s):  
J. P. Fawcett ◽  
J. F. Harrod
Keyword(s):  
Relative Rate ◽  
Oxidative Addition ◽  
Group Iv ◽  
Dominant Factor ◽  
Iridium Complex ◽  
Activation Entropy ◽  
Acid Base ◽  
Square Planar ◽  
The Difference ◽  
Kinetics Of

The kinetics of the reactions[Formula: see text]have been studied (M = Si, Ge, Sn). All three reactions proceed by predissociation of the iridium complex and concerted cis addition of Ph3MH to the square-planar intermediate. The relative rate of addition of Ph3MH increases in the order Si (1) < Ge (18) < Sn (70) and the difference in rate within experimental error is due entirely to change in ΔS0. It is concluded that, for this particular series of oxidative addition reactions, solvation effects related to a change in polarity on passage to the transition state are more important than bond energies, or acid–base properties, in determining relative reaction energetics. The relevance of entropy barriers to the problem of paraffin activation is discussed.

Acid-Catalyzed Oxidative Addition of a C–H Bond to a Square Planar d8 Iridium Complex

2014 ◽  
Vol 136 (25) ◽  
pp. 8891-8894 ◽  
Author(s):  
Jason D. Hackenberg ◽  
Sabuj Kundu ◽  
Thomas J. Emge ◽  
Karsten Krogh-Jespersen ◽  
Alan S. Goldman
Keyword(s):  
Oxidative Addition ◽  
Iridium Complex ◽  
Square Planar ◽  
Acid Catalyzed

Mathematical models of Gauss – Kruger projection for calculation of meridians conversion on the plane and scale of the image

2018 ◽  
Vol 934 (4) ◽  
pp. 2-7
Author(s):  
P.A. Medvedev ◽  
M.V. Novgorodskaya
Keyword(s):  
Mathematical Models ◽  
Analytical Methods ◽  
Theoretical Studies ◽  
Spherical Trigonometry ◽  
Cylindrical Projection ◽  
Rectangular Coordinates ◽  
In Series ◽  
Observational Errors ◽  
The Difference

This work contains continued research carried out on improving mathematical models of the Gauss-Krueger projection in accordance with the parameters of any ellipsoid with the removal of points from the axial meridian to l ≤ 6° . In terms of formulae earlier derived by the authors with improved convergence for the calculation of planar rectangular coordinates by geodesic coordinates, the algorithms for determining the convergence of meridians on the plane and the scale of the image are obtained. The improvement of the formulae represented in the form of series in powers of the difference in longitudes was accomplished by separating spherical terms in series and then replacing their approximate sums by exact expressions using the formulae of spherical trigonometry. As in previous works published in this journal [7, 8], determining the sums of the spherical terms was carried out according to the laws of the transverse-cylindrical projection of the sphere on the plane. Theoretical studies are given and formulae are proposed for estimating the observational errors in the results of the derived algorithms. The maximum of observational errors of convergence of meridians and scale, proceeding from the specified accuracy of the determined quantities was established through analytical methods.

THEORETICAL STUDIES ON THE COUPLING INTERACTIONS AND SELF-EXCHANGE REACTION MECHANISMS IN THE COMPLEXES OF NO WITH ONH AND NOH

2008 ◽  
Vol 07 (03) ◽  
pp. 435-446 ◽  
Author(s):  
PING LI ◽  
XIAOYAN XIE ◽  
YUXIANG BU ◽  
WEIHUA WANG ◽  
NANA WANG ◽  
...  
Keyword(s):  
Electron Transfer ◽  
Exchange Reaction ◽  
Reaction Mechanisms ◽  
Natural Bond Orbital ◽  
Theoretical Studies ◽  
Exchange Reactions ◽  
Electron Transfer Mechanism ◽  
Proton Coupled Electron Transfer ◽  
Planar Geometries ◽  
Transfer Mechanisms

The coupling interactions and self-exchange reaction mechanisms between NO and ONH (NOH) have been systematically investigated at the B3LYP/6-311++G** level of theory. All the equilibrium complexes are characterized by the intermolecular H-bonds and co-planar geometries. The cisoid NOH/ON species is the most stable one among all the complexes considered due to the formation of an N – N bond. Moreover, all the cisoid complexes are found to be more stable than the corresponding transoid ones. The origin of the blueshifts occurring in the selected complexes has been explored, employing the natural bond orbital (NBO) calculations. Additionally, the proton transfer mechanisms for the self-exchange reactions have been proposed, i.e. they can proceed via the three-center proton-coupled electron transfer or five-center cyclic proton-coupled electron transfer mechanism.

Experimental and theoretical studies on the oxidative addition of palladium(0) to β-chlorovinamidinium salts

Tetrahedron ◽  
2001 ◽  
Vol 57 (24) ◽  
pp. 5061-5066 ◽  
Author(s):  
Ian W Davies ◽  
Jimmy Wu ◽  
Jean-François Marcoux ◽  
Mark Taylor ◽  
David Hughes ◽  
...  
Keyword(s):  
Oxidative Addition ◽  
Theoretical Studies ◽  
Experimental And Theoretical Studies

Theoretical studies of the oxidative addition of PhBr to Pd(PX3)2 and Pd(X2PCH2CH2PX2) (X=Me, H, Cl)

2007 ◽  
Vol 692 (18) ◽  
pp. 3984-3993 ◽  
Author(s):  
Reza Fazaeli ◽  
Alireza Ariafard ◽  
Saiedeh Jamshidi ◽  
Elham S. Tabatabaie ◽  
Khatereh A. Pishro
Keyword(s):  
Oxidative Addition ◽  
Theoretical Studies
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