Nature of transmission of polar substituent effects in γ-disposed bicyclo[2.2.1]heptane (norbornane) and adamantane ring systems as monitored by 19F NMR: A DFT- GIAO and – NBO analysis

Adcock, William; Schamschurin, Andrew; Taylor, J. F.

doi:10.3998/ark.5550190.0010.504

Arkivoc

2008

DOI: 10.3998/ark.5550190.0010.504

|View full text |Cite

Nature of transmission of polar substituent effects in γ-disposed bicyclo[2.2.1]heptane (norbornane) and adamantane ring systems as monitored by 19F NMR: A DFT- GIAO and – NBO analysis

William Adcock¹,

Andrew Schamschurin²,

J. F. Taylor³

Help me understand this report

Search citation statements

Order By: Relevance

Paper Sections

Select...

Citation Types

Supporting

Mentioning

Contrasting

Year Published

2009

Publication Types

Select...

Article1

Relationship

Self Cite0

Independent1

Authors

Journals

Cited by 1 publication

References 4 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

Transmission of polar substituent effects across the cubane ring system: ¹⁹F substituent chemical shifts (SCS) of 4‐substituted (X) cub‐1‐yl fluorides revisited

Adcock

2009

J of Physical Organic Chem

View full text Add to dashboard Cite

Abstract19F NMR shieldings of 4‐substituted (X) cub‐1‐yl fluorides (4) for a set of substituents (XH, NO2, CN, NC, CF3, COOH, F, Cl, HO, NH2, CH3, Si(CH3)3, Li, O− and NH) covering a wide range of electronic substituent effects were calculated using the DFT‐GIAO theoretical model. The level of theory, B3LYP/6‐311+G(2d,p), provided 19F substituent chemical shifts (SCS) in good agreement with experimental values where known. By means of NBO analysis, various molecular parameters were obtained from the optimized geometries. Linear regression analysis was employed to explore the relationship between the calculated 19F SCS and polar field, resonance and group electronegativity substituent constants (σF, σR and σx, respectively) and also the NBO derived molecular parameters (fluorine natural charges (Qn), electron occupancies on fluorine of lone pairs (nF) and occupation number of the CF antibonding orbital (σCF*)). The key determining parameters appear to be nF and σCF*(occup). Both factors are a function of the electrostatic field influence of the substituent (σF effect) but are counteractive in their influence on the shifts. No evidence for a significant resonance effect influence on the shifts could be identified. Copyright © 2009 John Wiley & Sons, Ltd.

show abstract

Transmission of polar substituent effects across the cubane ring system: ¹⁹F substituent chemical shifts (SCS) of 4‐substituted (X) cub‐1‐yl fluorides revisited

Adcock

2009

J of Physical Organic Chem

View full text Add to dashboard Cite

show abstract

scite is a Brooklyn-based organization that helps researchers better discover and understand research articles through Smart Citations–citations that display the context of the citation and describe whether the article provides supporting or contrasting evidence. scite is used by students and researchers from around the world and is funded in part by the National Science Foundation and the National Institute on Drug Abuse of the National Institutes of Health.

Contact Info

hi@scite.ai

10624 S. Eastern Ave., Ste. A-614

Henderson, NV 89052, USA

Blog Terms and Conditions API Terms Privacy Policy Contact Cookie Preferences Do Not Sell or Share My Personal Information

Made with 💙 for researchers

Part of the Research Solutions Family.

Nature of transmission of polar substituent effects in γ-disposed bicyclo[2.2.1]heptane (norbornane) and adamantane ring systems as monitored by 19F NMR: A DFT- GIAO and – NBO analysis

Cited by 1 publication

References 4 publications

Transmission of polar substituent effects across the cubane ring system: ¹⁹F substituent chemical shifts (SCS) of 4‐substituted (X) cub‐1‐yl fluorides revisited

Transmission of polar substituent effects across the cubane ring system: ¹⁹F substituent chemical shifts (SCS) of 4‐substituted (X) cub‐1‐yl fluorides revisited

Contact Info

Product

Resources

About

Nature of transmission of polar substituent effects in γ-disposed bicyclo[2.2.1]heptane (norbornane) and adamantane ring systems as monitored by 19F NMR: A DFT- GIAO and – NBO analysis

Cited by 1 publication

References 4 publications

Transmission of polar substituent effects across the cubane ring system: 19F substituent chemical shifts (SCS) of 4‐substituted (X) cub‐1‐yl fluorides revisited

Transmission of polar substituent effects across the cubane ring system: 19F substituent chemical shifts (SCS) of 4‐substituted (X) cub‐1‐yl fluorides revisited

Contact Info

Product

Resources

About

Transmission of polar substituent effects across the cubane ring system: ¹⁹F substituent chemical shifts (SCS) of 4‐substituted (X) cub‐1‐yl fluorides revisited

Transmission of polar substituent effects across the cubane ring system: ¹⁹F substituent chemical shifts (SCS) of 4‐substituted (X) cub‐1‐yl fluorides revisited