Rate-Determining Role of Strain for Nitrogen Inversion in Polycyclic Tertiary Amines1

1996 ◽  
Vol 118 (33) ◽  
pp. 7783-7789 ◽  
Author(s):  
Anatoly M. Belostotskii ◽  
Hugo E. Gottlieb ◽  
Alfred Hassner
Keyword(s):  
Nitrogen Inversion

A molecular orbital study of the conformation (inversion and rotational barriers) and electronic properties of sulfamide

1989 ◽  
Vol 67 (12) ◽  
pp. 2227-2236 ◽  
Author(s):  
Otilia Mó ◽  
José L. G. De Paz ◽  
Manuel Yáñez ◽  
Ibon Alkorta ◽  
José Elguero ◽  
...  
Keyword(s):  
Multiple Bond ◽  
Amino Groups ◽  
Orbital Exponent ◽  
Nitrogen Inversion ◽  
Rotational Barriers ◽  
Polarization Functions ◽  
D Orbitals ◽  
Bond Character ◽  
Abinitio Calculations

Abinitio calculations have been used to study the conformational potential surface of sulfamide, by considering the S—N bond rotations and the nitrogen inversion processes. The lowest energy conformation (b) is found for a cis–trans arrangement of the amino groups, although conformations with cis–cis (a), trans–trans (c), and near staggered (c′) arrangements lie close in energy. Nitrogen inversion barriers are very low, and consequently one may expect forms b and c′ to be the only ones present in the gas phase. Conformer a is very polar, its dipole moment being twice that of b, so it may be favored in condensed media or in polar-solvent solutions. The relative stability of the different isomers is governed by interactions between the amino protons and between the nitrogen lone pairs. Our results show that d–π backbonding, involving the d orbitals on sulfur, is responsible for the multiple bond character of the S—O linkage, but is very small in the S—N interactions. The role of the sulfur d-orbital exponent, when a 6-31G* basis is used, is analyzed on a series of model compounds containing SII, SIV, and SVI. Although the inclusion of d functions on sulfur is crucial to describing correctly the bonding in sulfamide, the results obtained do not change appreciably if a second set of d functions is centered on sulfur. Nevertheless, only when polarization functions are also included for first-row atoms is the description of the system reliable. Keywords: sulfamide, inversion and rotational barriers, sulfur d-functions.

α- vs Ortho-Lithiation ofN-Alkylarylaziridines: Probing the Role of the Nitrogen Inversion Process†

2008 ◽  
Vol 73 (23) ◽  
pp. 9214-9220 ◽  
Author(s):  
Francesco Affortunato ◽  
Saverio Florio ◽  
Renzo Luisi ◽  
Biagia Musio
Keyword(s):  
Inversion Process ◽  
Nitrogen Inversion

Role of dactinomycin in the improved survival of children with Wilms' tumor

JAMA ◽  
1966 ◽  
Vol 195 (12) ◽  
pp. 1005-1009 ◽  
Author(s):  
D. J. Fernbach
Keyword(s):  
Wilms Tumor

Role of the allergist in diagnosis and management of patients with uveitis

JAMA ◽  
1966 ◽  
Vol 195 (3) ◽  
pp. 167-172 ◽  
Author(s):  
T. E. Van Metre
Keyword(s):  
Diagnosis And Management

The power of norms to sway fused group members

2018 ◽  
Vol 41 ◽  
Author(s):  
Winnifred R. Louis ◽  
Craig McGarty ◽  
Emma F. Thomas ◽  
Catherine E. Amiot ◽  
Fathali M. Moghaddam
Keyword(s):  
Evolutionary Anthropology ◽  
Normative Systems ◽  
Violent Extremism ◽  
Identity Fusion ◽  
Group Members

AbstractWhitehouse adapts insights from evolutionary anthropology to interpret extreme self-sacrifice through the concept of identity fusion. The model neglects the role of normative systems in shaping behaviors, especially in relation to violent extremism. In peaceful groups, increasing fusion will actually decrease extremism. Groups collectively appraise threats and opportunities, actively debate action options, and rarely choose violence toward self or others.

Elaborating the role of reflection and individual differences in the study of folk-economic beliefs

2018 ◽  
Vol 41 ◽  
Author(s):  
Kevin Arceneaux
Keyword(s):  
Decision Making ◽  
Individual Differences ◽  
Cognitive Processes ◽  
Evolutionary History ◽  
Behavioral Responses ◽  
History Of ◽  
Economic Beliefs

AbstractIntuitions guide decision-making, and looking to the evolutionary history of humans illuminates why some behavioral responses are more intuitive than others. Yet a place remains for cognitive processes to second-guess intuitive responses – that is, to be reflective – and individual differences abound in automatic, intuitive processing as well.

The role of affect in feelings of obligation

2020 ◽  
Vol 43 ◽  
Author(s):  
Stefen Beeler-Duden ◽  
Meltem Yucel ◽  
Amrisha Vaish
Keyword(s):  
Positive Emotions ◽  
The Creation ◽  
Sense Of Obligation

Abstract Tomasello offers a compelling account of the emergence of humans’ sense of obligation. We suggest that more needs to be said about the role of affect in the creation of obligations. We also argue that positive emotions such as gratitude evolved to encourage individuals to fulfill cooperative obligations without the negative quality that Tomasello proposes is inherent in obligations.

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