Synthesis, characterization, DFT calculations and antibacterial activity of palladium(II) cyanide complexes with thioamides

Saeed Ahmad; Shafqat Nadeem; Aneela Anwar; Abdul Hameed; Syed Ahmed Tirmizi; Wiktor Zierkiewicz; Azhar Abbas; Anvarhusein A. Isab; Mshari A. Alotaibi

doi:10.1016/j.molstruc.2017.03.098

Synthesis, characterization, DFT calculations and antibacterial activity of palladium(II) cyanide complexes with thioamides

Saeed Ahmad^*, Shafqat Nadeem, Aneela Anwar, Abdul Hameed, Syed Ahmed Tirmizi, Wiktor Zierkiewicz, Azhar Abbas, Anvarhusein A. Isab, Mshari A. Alotaibi

^*Corresponding author for this work

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

19 Scopus citations

Abstract

Palladium(II) cyanide complexes of thioamides (or thiones) having the general formula PdL₂(CN)₂, where L = Thiourea (Tu), Methylthiourea (Metu), N, N′-Dimethylthiourea (Dmtu), Tetramethylthiourea (Tmtu), 2-Mercaptopyridine (Mpy) and 2-Mercaptopyrimidine (Mpm) were prepared by reacting K₂[PdCl₄] with potassium cyanide and thioamides in the molar ratio of 1:2:2. The complexes were characterized by elemental analysis, thermal and spectroscopic methods (IR, ¹H and ¹³C NMR). The structures of three of the complexes were predicted by DFT calculations. The appearance of a band around 2100 cm⁻¹ in IR and resonances around 120–130 ppm in the ¹³C NMR spectra indicated the coordination of cyanide to palladium(II). More than one resonances were observed for CN⁻ carbon atoms in ¹³C NMR indicating the existence of equilibrium between different species in solution. DFT calculations revealed that in the case of the palladium(II) complex of Tmtu, the ionic dinuclear [Pd(Tmtu)₄][Pd(CN)₄] form was more stable than the dimer of mononuclear complex [Pd(Tmtu)₂(CN)₂] by 0.91 kcal mol⁻¹, while for the complexes of Tu or Mpy ligands, the nonionic [Pd(L)₂(CN)₂] forms were more stable than the corresponding [Pd(L)₄][Pd(CN)₄] complexes by 1.26 and 6.49 kcal mol⁻¹ for L = Tu and Mpy, respectively. The complexes were screened for antibacterial effects and some of them showed significant activities against both gram positive as well as gram negative bacteria.

Original language	English
Pages (from-to)	204-212
Number of pages	9
Journal	Journal of Molecular Structure
Volume	1141
DOIs	https://doi.org/10.1016/j.molstruc.2017.03.098
State	Published - 5 Aug 2017

Bibliographical note

Publisher Copyright:
© 2017 Elsevier B.V.

Keywords

Antimicrobial
Cyanide
DFT calculations
Palladium(II) complexes
Thioamide

ASJC Scopus subject areas

Analytical Chemistry
Spectroscopy
Organic Chemistry
Inorganic Chemistry

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10.1016/j.molstruc.2017.03.098

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@article{7045c08db8b945dd852381ebbee46c41,

title = "Synthesis, characterization, DFT calculations and antibacterial activity of palladium(II) cyanide complexes with thioamides",

abstract = "Palladium(II) cyanide complexes of thioamides (or thiones) having the general formula PdL2(CN)2, where L = Thiourea (Tu), Methylthiourea (Metu), N, N′-Dimethylthiourea (Dmtu), Tetramethylthiourea (Tmtu), 2-Mercaptopyridine (Mpy) and 2-Mercaptopyrimidine (Mpm) were prepared by reacting K2[PdCl4] with potassium cyanide and thioamides in the molar ratio of 1:2:2. The complexes were characterized by elemental analysis, thermal and spectroscopic methods (IR, 1H and 13C NMR). The structures of three of the complexes were predicted by DFT calculations. The appearance of a band around 2100 cm−1 in IR and resonances around 120–130 ppm in the 13C NMR spectra indicated the coordination of cyanide to palladium(II). More than one resonances were observed for CN− carbon atoms in 13C NMR indicating the existence of equilibrium between different species in solution. DFT calculations revealed that in the case of the palladium(II) complex of Tmtu, the ionic dinuclear [Pd(Tmtu)4][Pd(CN)4] form was more stable than the dimer of mononuclear complex [Pd(Tmtu)2(CN)2] by 0.91 kcal mol−1, while for the complexes of Tu or Mpy ligands, the nonionic [Pd(L)2(CN)2] forms were more stable than the corresponding [Pd(L)4][Pd(CN)4] complexes by 1.26 and 6.49 kcal mol−1 for L = Tu and Mpy, respectively. The complexes were screened for antibacterial effects and some of them showed significant activities against both gram positive as well as gram negative bacteria.",

keywords = "Antimicrobial, Cyanide, DFT calculations, Palladium(II) complexes, Thioamide",

author = "Saeed Ahmad and Shafqat Nadeem and Aneela Anwar and Abdul Hameed and Tirmizi, {Syed Ahmed} and Wiktor Zierkiewicz and Azhar Abbas and Isab, {Anvarhusein A.} and Alotaibi, {Mshari A.}",

note = "Publisher Copyright: {\textcopyright} 2017 Elsevier B.V.",

year = "2017",

month = aug,

day = "5",

doi = "10.1016/j.molstruc.2017.03.098",

language = "English",

volume = "1141",

pages = "204--212",

journal = "Journal of Molecular Structure",

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TY - JOUR

T1 - Synthesis, characterization, DFT calculations and antibacterial activity of palladium(II) cyanide complexes with thioamides

AU - Ahmad, Saeed

AU - Nadeem, Shafqat

AU - Anwar, Aneela

AU - Hameed, Abdul

AU - Tirmizi, Syed Ahmed

AU - Zierkiewicz, Wiktor

AU - Abbas, Azhar

AU - Isab, Anvarhusein A.

AU - Alotaibi, Mshari A.

PY - 2017/8/5

Y1 - 2017/8/5

N2 - Palladium(II) cyanide complexes of thioamides (or thiones) having the general formula PdL2(CN)2, where L = Thiourea (Tu), Methylthiourea (Metu), N, N′-Dimethylthiourea (Dmtu), Tetramethylthiourea (Tmtu), 2-Mercaptopyridine (Mpy) and 2-Mercaptopyrimidine (Mpm) were prepared by reacting K2[PdCl4] with potassium cyanide and thioamides in the molar ratio of 1:2:2. The complexes were characterized by elemental analysis, thermal and spectroscopic methods (IR, 1H and 13C NMR). The structures of three of the complexes were predicted by DFT calculations. The appearance of a band around 2100 cm−1 in IR and resonances around 120–130 ppm in the 13C NMR spectra indicated the coordination of cyanide to palladium(II). More than one resonances were observed for CN− carbon atoms in 13C NMR indicating the existence of equilibrium between different species in solution. DFT calculations revealed that in the case of the palladium(II) complex of Tmtu, the ionic dinuclear [Pd(Tmtu)4][Pd(CN)4] form was more stable than the dimer of mononuclear complex [Pd(Tmtu)2(CN)2] by 0.91 kcal mol−1, while for the complexes of Tu or Mpy ligands, the nonionic [Pd(L)2(CN)2] forms were more stable than the corresponding [Pd(L)4][Pd(CN)4] complexes by 1.26 and 6.49 kcal mol−1 for L = Tu and Mpy, respectively. The complexes were screened for antibacterial effects and some of them showed significant activities against both gram positive as well as gram negative bacteria.

AB - Palladium(II) cyanide complexes of thioamides (or thiones) having the general formula PdL2(CN)2, where L = Thiourea (Tu), Methylthiourea (Metu), N, N′-Dimethylthiourea (Dmtu), Tetramethylthiourea (Tmtu), 2-Mercaptopyridine (Mpy) and 2-Mercaptopyrimidine (Mpm) were prepared by reacting K2[PdCl4] with potassium cyanide and thioamides in the molar ratio of 1:2:2. The complexes were characterized by elemental analysis, thermal and spectroscopic methods (IR, 1H and 13C NMR). The structures of three of the complexes were predicted by DFT calculations. The appearance of a band around 2100 cm−1 in IR and resonances around 120–130 ppm in the 13C NMR spectra indicated the coordination of cyanide to palladium(II). More than one resonances were observed for CN− carbon atoms in 13C NMR indicating the existence of equilibrium between different species in solution. DFT calculations revealed that in the case of the palladium(II) complex of Tmtu, the ionic dinuclear [Pd(Tmtu)4][Pd(CN)4] form was more stable than the dimer of mononuclear complex [Pd(Tmtu)2(CN)2] by 0.91 kcal mol−1, while for the complexes of Tu or Mpy ligands, the nonionic [Pd(L)2(CN)2] forms were more stable than the corresponding [Pd(L)4][Pd(CN)4] complexes by 1.26 and 6.49 kcal mol−1 for L = Tu and Mpy, respectively. The complexes were screened for antibacterial effects and some of them showed significant activities against both gram positive as well as gram negative bacteria.

KW - Antimicrobial

KW - Cyanide

KW - DFT calculations

KW - Palladium(II) complexes

KW - Thioamide

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U2 - 10.1016/j.molstruc.2017.03.098

DO - 10.1016/j.molstruc.2017.03.098

M3 - Article

AN - SCOPUS:85016570904

SN - 0022-2860

VL - 1141

SP - 204

EP - 212

JO - Journal of Molecular Structure

JF - Journal of Molecular Structure

ER -

Synthesis, characterization, DFT calculations and antibacterial activity of palladium(II) cyanide complexes with thioamides

Abstract

Bibliographical note

Keywords

ASJC Scopus subject areas

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