Novel N-heterocyclic Stannylenes (NHSns) using DFT

Amir Hosein Zamanzadeh; Nazanin Mohebi; Mohamad Zaman Kassaee; P. T. Cummings; Kun Dong

doi:10.22036/pcr.2019.172684.1597

Novel N-heterocyclic Stannylenes (NHSns) using DFT

Amir Hosein Zamanzadeh
, Nazanin Mohebi
, Mohamad Zaman Kassaee^*
, P. T. Cummings
, Kun Dong

^*Corresponding author for this work

Research output: Contribution to journal › Article › peer-review

1 Citation (Scopus)

6 Downloads (Pure)

Abstract

Substitution effects are probed for novel N-heterocyclic stannylenes (NHSns), including 1,4-di(R)-tetrazole-5-stannylenes (1_R), and 1,3-di(R)-tetrazole-5-stannylenes (2_R), using B3LYP/6-311++G** level of theory. Nucleophilicity, multiplicity, and stability are calculated for 1_R and 2_R; R = H, methyl, ethyl, i-propyl, t-butyl, Ph, OH, methoxy, NO₂, CN and CF₃. Asymmetric 2_H appears to be more nucleophilic (N ~ 4) than its corresponding symmetric 1_H isomer (N ~ 3), mostly due to the higher separation of charge in the former group. The N is more sensitive to electronic effects in 1_R stannylenes than those in the 2_R series. Electron donating R groups increase N with Hammett ρ constants of -3.3 and -2.7 for 1_R and 2_R, respectively. Stannylene 2_H is slightly more aromatic (NICS (1) = -10.31) than 1_H (NICS (1) = -10.25). All 1_R isomers are more stable than the corresponding 2_R. However, all 2_R structures are generally more nucleophilic and aromatic than the corresponding 1_R. In addition, the former is less electrophilic with a larger band gap and narrower stannylene bond angle. Substituent effects are probed on N by devising proper isodesmic reactions. The trend for N is: 2_t-buthyl > 2_iso-propyl > 2_ethyl > 2_methyl > 2_ph > 2_OMeth > 1_t-buthyl > 2_OH > 2_H > 1_Ph > 1_iso-propyl > 1_OH > 1_ethyl > 1_methyl > 1_OMeth > 1_H > 2CF₃ > 2_NO2 > 2_CN > 1_CF3 > 1_CN > 1_NO2.

Original language	English
Pages (from-to)	511-521
Number of pages	11
Journal	Physical Chemistry Research
Volume	7
Issue number	3
DOIs	https://doi.org/10.22036/pcr.2019.172684.1597
Publication status	Published - Sept 2019

Keywords

DFT
N-Heterocyclic
Nucleophilicity
Stannylenes

ASJC Scopus subject areas

Statistical and Nonlinear Physics
Fluid Flow and Transfer Processes
Physical and Theoretical Chemistry

Access to Document

10.22036/pcr.2019.172684.1597Licence: CC BY

Download pdf
Access The full text of all published articles is freely available on the journal website (https://www.physchemres.org) under the Creative Commons Attribution 4.0 International License.
Final published version, 1.17 MBLicence: CC BY

Cite this

@article{da60e31a1b56441bb7b932a0d94c8bd8,

title = "Novel N-heterocyclic Stannylenes (NHSns) using DFT",

abstract = "Substitution effects are probed for novel N-heterocyclic stannylenes (NHSns), including 1,4-di(R)-tetrazole-5-stannylenes (1R), and 1,3-di(R)-tetrazole-5-stannylenes (2R), using B3LYP/6-311++G** level of theory. Nucleophilicity, multiplicity, and stability are calculated for 1R and 2R; R = H, methyl, ethyl, i-propyl, t-butyl, Ph, OH, methoxy, NO2, CN and CF3. Asymmetric 2H appears to be more nucleophilic (N \textasciitilde{} 4) than its corresponding symmetric 1H isomer (N \textasciitilde{} 3), mostly due to the higher separation of charge in the former group. The N is more sensitive to electronic effects in 1R stannylenes than those in the 2R series. Electron donating R groups increase N with Hammett ρ constants of -3.3 and -2.7 for 1R and 2R, respectively. Stannylene 2H is slightly more aromatic (NICS (1) = -10.31) than 1H (NICS (1) = -10.25). All 1R isomers are more stable than the corresponding 2R. However, all 2R structures are generally more nucleophilic and aromatic than the corresponding 1R. In addition, the former is less electrophilic with a larger band gap and narrower stannylene bond angle. Substituent effects are probed on N by devising proper isodesmic reactions. The trend for N is: 2t-buthyl > 2iso-propyl > 2ethyl > 2methyl > 2ph > 2OMeth > 1t-buthyl > 2OH > 2H > 1Ph > 1iso-propyl > 1OH > 1ethyl > 1methyl > 1OMeth > 1H > 2CF3 > 2NO2 > 2CN > 1CF3 > 1CN > 1NO2.",

keywords = "DFT, N-Heterocyclic, Nucleophilicity, Stannylenes",

author = "Zamanzadeh, \{Amir Hosein\} and Nazanin Mohebi and Kassaee, \{Mohamad Zaman\} and Cummings, \{P. T.\} and Kun Dong",

note = "Publisher Copyright: {\textcopyright} 2019, Iranian Chemical Society.",

year = "2019",

month = sep,

doi = "10.22036/pcr.2019.172684.1597",

language = "English",

volume = "7",

pages = "511--521",

journal = "Physical Chemistry Research",

issn = "2322-5521",

publisher = "Iranian Chemical Society",

number = "3",

}

TY - JOUR

T1 - Novel N-heterocyclic Stannylenes (NHSns) using DFT

AU - Zamanzadeh, Amir Hosein

AU - Mohebi, Nazanin

AU - Kassaee, Mohamad Zaman

AU - Cummings, P. T.

AU - Dong, Kun

PY - 2019/9

Y1 - 2019/9

N2 - Substitution effects are probed for novel N-heterocyclic stannylenes (NHSns), including 1,4-di(R)-tetrazole-5-stannylenes (1R), and 1,3-di(R)-tetrazole-5-stannylenes (2R), using B3LYP/6-311++G** level of theory. Nucleophilicity, multiplicity, and stability are calculated for 1R and 2R; R = H, methyl, ethyl, i-propyl, t-butyl, Ph, OH, methoxy, NO2, CN and CF3. Asymmetric 2H appears to be more nucleophilic (N ~ 4) than its corresponding symmetric 1H isomer (N ~ 3), mostly due to the higher separation of charge in the former group. The N is more sensitive to electronic effects in 1R stannylenes than those in the 2R series. Electron donating R groups increase N with Hammett ρ constants of -3.3 and -2.7 for 1R and 2R, respectively. Stannylene 2H is slightly more aromatic (NICS (1) = -10.31) than 1H (NICS (1) = -10.25). All 1R isomers are more stable than the corresponding 2R. However, all 2R structures are generally more nucleophilic and aromatic than the corresponding 1R. In addition, the former is less electrophilic with a larger band gap and narrower stannylene bond angle. Substituent effects are probed on N by devising proper isodesmic reactions. The trend for N is: 2t-buthyl > 2iso-propyl > 2ethyl > 2methyl > 2ph > 2OMeth > 1t-buthyl > 2OH > 2H > 1Ph > 1iso-propyl > 1OH > 1ethyl > 1methyl > 1OMeth > 1H > 2CF3 > 2NO2 > 2CN > 1CF3 > 1CN > 1NO2.

AB - Substitution effects are probed for novel N-heterocyclic stannylenes (NHSns), including 1,4-di(R)-tetrazole-5-stannylenes (1R), and 1,3-di(R)-tetrazole-5-stannylenes (2R), using B3LYP/6-311++G** level of theory. Nucleophilicity, multiplicity, and stability are calculated for 1R and 2R; R = H, methyl, ethyl, i-propyl, t-butyl, Ph, OH, methoxy, NO2, CN and CF3. Asymmetric 2H appears to be more nucleophilic (N ~ 4) than its corresponding symmetric 1H isomer (N ~ 3), mostly due to the higher separation of charge in the former group. The N is more sensitive to electronic effects in 1R stannylenes than those in the 2R series. Electron donating R groups increase N with Hammett ρ constants of -3.3 and -2.7 for 1R and 2R, respectively. Stannylene 2H is slightly more aromatic (NICS (1) = -10.31) than 1H (NICS (1) = -10.25). All 1R isomers are more stable than the corresponding 2R. However, all 2R structures are generally more nucleophilic and aromatic than the corresponding 1R. In addition, the former is less electrophilic with a larger band gap and narrower stannylene bond angle. Substituent effects are probed on N by devising proper isodesmic reactions. The trend for N is: 2t-buthyl > 2iso-propyl > 2ethyl > 2methyl > 2ph > 2OMeth > 1t-buthyl > 2OH > 2H > 1Ph > 1iso-propyl > 1OH > 1ethyl > 1methyl > 1OMeth > 1H > 2CF3 > 2NO2 > 2CN > 1CF3 > 1CN > 1NO2.

KW - DFT

KW - N-Heterocyclic

KW - Nucleophilicity

KW - Stannylenes

UR - https://www.scopus.com/pages/publications/85075185680

U2 - 10.22036/pcr.2019.172684.1597

DO - 10.22036/pcr.2019.172684.1597

M3 - Article

AN - SCOPUS:85075185680

SN - 2322-5521

VL - 7

SP - 511

EP - 521

JO - Physical Chemistry Research

JF - Physical Chemistry Research

IS - 3

ER -

Novel N-heterocyclic Stannylenes (NHSns) using DFT

Abstract

Keywords

ASJC Scopus subject areas

Access to Document

Other files and links

Fingerprint

Cite this