AM1 and PM3 semiempirical calculations on 1-aryl-3,3-diethyltriazenes: correlation of bond orders with rotational barriers and quantum yields of photolysis

1993 ◽  
Vol 97 (20) ◽  
pp. 5246-5253 ◽  
Author(s):  
J. C. Panitz ◽  
T. Lippert ◽  
J. Stebani ◽  
O. Nuyken ◽  
A. Wokaun
Keyword(s):  
Semiempirical Calculations ◽  
Quantum Yields ◽  
Bond Orders ◽  
Rotational Barriers ◽  
Pm3 Semiempirical Calculations

Highly Luminescent 4-Pyridyl-Extended Dithieno[3,2-b:2′,3′-d]phospholes

2020 ◽  
Author(s):  
Thomas Baumgartner ◽  
Paul Demay-Drouhard
Keyword(s):  
Electrochemical Properties ◽  
Quantum Yields

The unexpectedly challenging synthesis of 4-pyridyl-extended dithienophospholes is reported. The optical and electrochemical properties of the phosphoryl-bridged species were studied experimentally and computationally, and their properties compared to their non-<i>P</i>-bridged congeners. The 4-pyridyl-extended dithieno-phospholes display quantitative luminescence quantum yields in solution.<br><br>

Highly Luminescent 4-Pyridyl-Extended Dithieno[3,2-b:2′,3′-d]phospholes

2020 ◽  
Author(s):  
Thomas Baumgartner ◽  
Paul Demay-Drouhard
Keyword(s):  
Electrochemical Properties ◽  
Quantum Yields

The unexpectedly challenging synthesis of 4-pyridyl-extended dithienophospholes is reported. The optical and electrochemical properties of the phosphoryl-bridged species were studied experimentally and computationally, and their properties compared to their non-<i>P</i>-bridged congeners. The 4-pyridyl-extended dithieno-phospholes display quantitative luminescence quantum yields in solution.<br><br>

Catalyst-Control over Sixfold Stereogenicity

2020 ◽  
Author(s):  
Xingxing Wu ◽  
Reto M. Witzig ◽  
Rodolphe Beaud ◽  
Christian Fischer ◽  
Daniel Häussinger ◽  
...  
Keyword(s):  
Conformational Analysis ◽  
Higher Order ◽  
Binary Codes ◽  
Rotational Barriers ◽  
Molecular Architectures

Governing higher-order stereogenicity is a long-standing goal in stereoselective catalysis, because it allows to achieve selectivity for more than a twofold number of stereoisomers per stereogenic unit. Current methods warrant control over the power of two stereoisomers and the configurations are routinely assigned using the descriptors ( R ) and ( S ), or related binary codes. In contrast, conformational analysis ranges beyond this dualistic treatment of stereoisomerism, which constitutes an unmet challenge for catalyst stereocontrolled processes. Herein, we now report that sixfold stereogenicity can be governed by stereoselective catalysis. By controlling a configurationally stable stereogenic axis with six large rotational barriers, a catalytic [2+2+2]-cyclotrimerization selectively governs the formation of one out of six stereoisomers with up to 0:0:2:98:0:0 stereocontrol. The underpinnings of conformational analysis and stereoselective catalysis are thereby conceptually reunited. Novel molecular architectures featuring distinct chemical topologies and unexplored chemical designs are anticipated from catalystcontrol over higher-order stereogenicities

The Nature of S-N Bonding in Sulfonamides and Related Compounds: Insights into π-Bonding Contributions from Sulfur K-Edge XAS

2020 ◽  
Author(s):  
Tulin Okbinoglu ◽  
Pierre Kennepohl
Keyword(s):  
Density Functional ◽  
Chemical Properties ◽  
Functional Theory ◽  
Rotational Barriers ◽  
Td Dft ◽  
Nitrogen Bonds ◽  
X Ray Absorption ◽  
Related Compounds ◽  
And Chemical Properties

Molecules containing sulfur-nitrogen bonds, like sulfonamides, have long been of interest due to their many uses and chemical properties. Understanding the factors that cause sulfonamide reactivity is important, yet their continues to be controversy regarding the relevance of S-N π bonding in describing these species. In this paper, we use sulfur K-edge x-ray absorption spectroscopy (XAS) in conjunction with density functional theory (DFT) to explore the role of S<sub>3p</sub> contributions to π-bonding in sulfonamides, sulfinamides and sulfenamides. We explore the nature of electron distribution of the sulfur atom and its nearest neighbors and extend the scope to explore the effects on rotational barriers along the sulfur-nitrogen axis. The experimental XAS data together with TD-DFT calculations confirm that sulfonamides, and the other sulfinated amides in this series, have essentially no S-N π bonding involving S<sub>3p</sub> contributions and that electron repulsion and is the dominant force that affect rotational barriers.

Sign in / Sign up

Export Citation Format

Share Document