Periodic DFT modeling and vibrational analysis of silver(I) cyanide complexes of thioureas

Saeed Ahmad; Ivelina Georgieva; Muhammad Hanif; Muhammad Monim-ul-Mehboob; Shaukat Munir; Ahsan Sohail; Anvarhusein A. Isab

doi:10.1007/s00894-019-3970-2

Periodic DFT modeling and vibrational analysis of silver(I) cyanide complexes of thioureas

Saeed Ahmad^*, Ivelina Georgieva, Muhammad Hanif, Muhammad Monim-ul-Mehboob, Shaukat Munir, Ahsan Sohail, Anvarhusein A. Isab

^*Corresponding author for this work

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

10 Scopus citations

Abstract

The structures of non-ionic [Ag(Tu)(CN)] (1) and ionic [Ag(Dmtu)₂]⁺[Ag(CN)₂]⁻ (2) and [Ag(Imt)₂]⁺[Ag(CN)₂]⁻ (3) silver(I) complexes, where Tu = thiourea, Dmtu = N,N′-dimethylthiourea and Imt = imidazoline-2-thione), were modeled by periodic DFT/PAW-PBE calculations; results were in good agreement with experiments. The bonding ability of the thiourea ligands (Tu, Dmtu and Imt) and the rival Ag–C, Ag–S, Ag–N and Ag–Ag bonds were estimated by natural population analysis and natural bonding orbital calculations. The metal–ligand bond strengths were found to decrease in the following order Ag-C_CN > Ag-S_thiourea > Ag–N_CN, and the main bonding contribution was covalent, donor–acceptor and electrostatic, respectively. The non-ionic [Ag(Tu)(CN)] complex formation [distinguished from the ionic Ag(I) complexes] was explained with the largest bonding capacity of the sulfur donor atom of Tu ligand and the strongest covalent and donor-acceptor Ag–S(Tu) interaction. The infrared (IR) spectra of the experimentally observed structures were reliably interpreted and the IR vibrations, which were sensitive to the ligand coordination to Ag(I) ion and to the weak intra- and intermolecular interactions, were selected with the help of DFT frequency calculations in the solid state. [Figure not available: see fulltext.].

Original language	English
Article number	90
Journal	Journal of Molecular Modeling
Volume	25
Issue number	4
DOIs	https://doi.org/10.1007/s00894-019-3970-2
State	Published - 1 Apr 2019

Bibliographical note

Publisher Copyright:
© 2019, Springer-Verlag GmbH Germany, part of Springer Nature.

Keywords

Cyanide
Periodic DFT calculations
Silver(I) complexes
Thiourea

ASJC Scopus subject areas

Catalysis
Computer Science Applications
Physical and Theoretical Chemistry
Organic Chemistry
Inorganic Chemistry
Computational Theory and Mathematics

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10.1007/s00894-019-3970-2

Cite this

@article{17384bb9f6444a8db7ae0e8961d7befc,

title = "Periodic DFT modeling and vibrational analysis of silver(I) cyanide complexes of thioureas",

abstract = "The structures of non-ionic [Ag(Tu)(CN)] (1) and ionic [Ag(Dmtu)2]+[Ag(CN)2]− (2) and [Ag(Imt)2]+[Ag(CN)2]− (3) silver(I) complexes, where Tu = thiourea, Dmtu = N,N′-dimethylthiourea and Imt = imidazoline-2-thione), were modeled by periodic DFT/PAW-PBE calculations; results were in good agreement with experiments. The bonding ability of the thiourea ligands (Tu, Dmtu and Imt) and the rival Ag–C, Ag–S, Ag–N and Ag–Ag bonds were estimated by natural population analysis and natural bonding orbital calculations. The metal–ligand bond strengths were found to decrease in the following order Ag-CCN > Ag-Sthiourea > Ag–NCN, and the main bonding contribution was covalent, donor–acceptor and electrostatic, respectively. The non-ionic [Ag(Tu)(CN)] complex formation [distinguished from the ionic Ag(I) complexes] was explained with the largest bonding capacity of the sulfur donor atom of Tu ligand and the strongest covalent and donor-acceptor Ag–S(Tu) interaction. The infrared (IR) spectra of the experimentally observed structures were reliably interpreted and the IR vibrations, which were sensitive to the ligand coordination to Ag(I) ion and to the weak intra- and intermolecular interactions, were selected with the help of DFT frequency calculations in the solid state. [Figure not available: see fulltext.].",

keywords = "Cyanide, Periodic DFT calculations, Silver(I) complexes, Thiourea",

author = "Saeed Ahmad and Ivelina Georgieva and Muhammad Hanif and Muhammad Monim-ul-Mehboob and Shaukat Munir and Ahsan Sohail and Isab, \{Anvarhusein A.\}",

note = "Publisher Copyright: {\textcopyright} 2019, Springer-Verlag GmbH Germany, part of Springer Nature.",

year = "2019",

month = apr,

day = "1",

doi = "10.1007/s00894-019-3970-2",

language = "English",

volume = "25",

journal = "Journal of Molecular Modeling",

issn = "1610-2940",

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TY - JOUR

T1 - Periodic DFT modeling and vibrational analysis of silver(I) cyanide complexes of thioureas

AU - Ahmad, Saeed

AU - Georgieva, Ivelina

AU - Hanif, Muhammad

AU - Monim-ul-Mehboob, Muhammad

AU - Munir, Shaukat

AU - Sohail, Ahsan

AU - Isab, Anvarhusein A.

PY - 2019/4/1

Y1 - 2019/4/1

N2 - The structures of non-ionic [Ag(Tu)(CN)] (1) and ionic [Ag(Dmtu)2]+[Ag(CN)2]− (2) and [Ag(Imt)2]+[Ag(CN)2]− (3) silver(I) complexes, where Tu = thiourea, Dmtu = N,N′-dimethylthiourea and Imt = imidazoline-2-thione), were modeled by periodic DFT/PAW-PBE calculations; results were in good agreement with experiments. The bonding ability of the thiourea ligands (Tu, Dmtu and Imt) and the rival Ag–C, Ag–S, Ag–N and Ag–Ag bonds were estimated by natural population analysis and natural bonding orbital calculations. The metal–ligand bond strengths were found to decrease in the following order Ag-CCN > Ag-Sthiourea > Ag–NCN, and the main bonding contribution was covalent, donor–acceptor and electrostatic, respectively. The non-ionic [Ag(Tu)(CN)] complex formation [distinguished from the ionic Ag(I) complexes] was explained with the largest bonding capacity of the sulfur donor atom of Tu ligand and the strongest covalent and donor-acceptor Ag–S(Tu) interaction. The infrared (IR) spectra of the experimentally observed structures were reliably interpreted and the IR vibrations, which were sensitive to the ligand coordination to Ag(I) ion and to the weak intra- and intermolecular interactions, were selected with the help of DFT frequency calculations in the solid state. [Figure not available: see fulltext.].

AB - The structures of non-ionic [Ag(Tu)(CN)] (1) and ionic [Ag(Dmtu)2]+[Ag(CN)2]− (2) and [Ag(Imt)2]+[Ag(CN)2]− (3) silver(I) complexes, where Tu = thiourea, Dmtu = N,N′-dimethylthiourea and Imt = imidazoline-2-thione), were modeled by periodic DFT/PAW-PBE calculations; results were in good agreement with experiments. The bonding ability of the thiourea ligands (Tu, Dmtu and Imt) and the rival Ag–C, Ag–S, Ag–N and Ag–Ag bonds were estimated by natural population analysis and natural bonding orbital calculations. The metal–ligand bond strengths were found to decrease in the following order Ag-CCN > Ag-Sthiourea > Ag–NCN, and the main bonding contribution was covalent, donor–acceptor and electrostatic, respectively. The non-ionic [Ag(Tu)(CN)] complex formation [distinguished from the ionic Ag(I) complexes] was explained with the largest bonding capacity of the sulfur donor atom of Tu ligand and the strongest covalent and donor-acceptor Ag–S(Tu) interaction. The infrared (IR) spectra of the experimentally observed structures were reliably interpreted and the IR vibrations, which were sensitive to the ligand coordination to Ag(I) ion and to the weak intra- and intermolecular interactions, were selected with the help of DFT frequency calculations in the solid state. [Figure not available: see fulltext.].

KW - Cyanide

KW - Periodic DFT calculations

KW - Silver(I) complexes

KW - Thiourea

UR - https://www.scopus.com/pages/publications/85062636635

U2 - 10.1007/s00894-019-3970-2

DO - 10.1007/s00894-019-3970-2

M3 - Article

C2 - 30847580

AN - SCOPUS:85062636635

SN - 1610-2940

VL - 25

JO - Journal of Molecular Modeling

JF - Journal of Molecular Modeling

IS - 4

M1 - 90

ER -

Periodic DFT modeling and vibrational analysis of silver(I) cyanide complexes of thioureas

Abstract

Bibliographical note

Keywords

ASJC Scopus subject areas

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