Synthesis, structure, theoretical studies and electrochemistry of Ru(II)–N heterocyclic carbenes

Lakshmikanta Maity; Sirsendu Das Adhikary; Ambarish Mondal; Hemanta K. Kisan; Anvarhusein A. Isab; Shyamaprosad Goswami; Joydev Dinda

doi:10.1016/j.ica.2018.04.029

Synthesis, structure, theoretical studies and electrochemistry of Ru(II)–N heterocyclic carbenes

Lakshmikanta Maity
, Sirsendu Das Adhikary
, Ambarish Mondal
, Hemanta K. Kisan
, Anvarhusein A. Isab
, Shyamaprosad Goswami
, Joydev Dinda^*

^*Corresponding author for this work

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

8 Scopus citations

Abstract

Synthesis, structure, electrochemistry and theoretical studies of Ru(II) complexes, 1-(2-Pyrimidyl)-3-(methyl) imidazoline-2-ylidene tetraacetonitrileruthenium(II)hexafluorophosphate, 2 and 1-(2-Pyrimidyl)-3-(methyl)benzimidazoline-2-ylidene tetraacetonitrileruthenium(II)hexafluorophosphate, 4 bearing pyrimidine functionalized C,N donor N-heterocyclic carbene proligands 1-(2-Pyrimidyl)-3-(methyl)imidazolium hexafluorophosphate; 1-H(PF₆) and 1-(2-Pyrimidyl)-3-(methyl)benzimidazolium hexafluorophosphate; 3-H(PF₆) have been reported. The compounds were fully characterized by elemental analysis, NMR, UV–Vis spectroscopy and finally the solid state structure of 2 is confirmed by X-ray diffraction studies. Theoretically geometry of complex 4 is optimized using B3LYP-D3/def2-TZVP. Natural Bond Orbital (NBO) analysis of complexes 2 and 4 support the π-back bonding Ru → N[dbnd]C_carbene. Cyclic voltammetry studies revealed Ru(II)/Ru(III) reversible oxidation couple at 0.50 and 0.52 eV respectively for complexes 2 and 4; the higher oxidation potential of 4 compared to 2 is assigned due to π-acid character of benzimidazole.

Original language	English
Pages (from-to)	141-147
Number of pages	7
Journal	Inorganica Chimica Acta
Volume	479
DOIs	https://doi.org/10.1016/j.ica.2018.04.029
State	Published - 1 Jul 2018

Bibliographical note

Publisher Copyright:
© 2018 Elsevier B.V.

Keywords

Electrochemistry
N-heterocyclic carbene
Pyrimidine
Ruthenium-NHC
X-ray structure

ASJC Scopus subject areas

Physical and Theoretical Chemistry
Inorganic Chemistry
Materials Chemistry

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10.1016/j.ica.2018.04.029

Cite this

@article{7ec4a51fdea24e1f81e1a6d1c4b05e88,

title = "Synthesis, structure, theoretical studies and electrochemistry of Ru(II)–N heterocyclic carbenes",

abstract = "Synthesis, structure, electrochemistry and theoretical studies of Ru(II) complexes, 1-(2-Pyrimidyl)-3-(methyl) imidazoline-2-ylidene tetraacetonitrileruthenium(II)hexafluorophosphate, 2 and 1-(2-Pyrimidyl)-3-(methyl)benzimidazoline-2-ylidene tetraacetonitrileruthenium(II)hexafluorophosphate, 4 bearing pyrimidine functionalized C,N donor N-heterocyclic carbene proligands 1-(2-Pyrimidyl)-3-(methyl)imidazolium hexafluorophosphate; 1-H(PF6) and 1-(2-Pyrimidyl)-3-(methyl)benzimidazolium hexafluorophosphate; 3-H(PF6) have been reported. The compounds were fully characterized by elemental analysis, NMR, UV–Vis spectroscopy and finally the solid state structure of 2 is confirmed by X-ray diffraction studies. Theoretically geometry of complex 4 is optimized using B3LYP-D3/def2-TZVP. Natural Bond Orbital (NBO) analysis of complexes 2 and 4 support the π-back bonding Ru → N[dbnd]Ccarbene. Cyclic voltammetry studies revealed Ru(II)/Ru(III) reversible oxidation couple at 0.50 and 0.52 eV respectively for complexes 2 and 4; the higher oxidation potential of 4 compared to 2 is assigned due to π-acid character of benzimidazole.",

keywords = "Electrochemistry, N-heterocyclic carbene, Pyrimidine, Ruthenium-NHC, X-ray structure",

author = "Lakshmikanta Maity and \{Das Adhikary\}, Sirsendu and Ambarish Mondal and Kisan, \{Hemanta K.\} and Isab, \{Anvarhusein A.\} and Shyamaprosad Goswami and Joydev Dinda",

note = "Publisher Copyright: {\textcopyright} 2018 Elsevier B.V.",

year = "2018",

month = jul,

day = "1",

doi = "10.1016/j.ica.2018.04.029",

language = "English",

volume = "479",

pages = "141--147",

journal = "Inorganica Chimica Acta",

issn = "0020-1693",

publisher = "Elsevier BV",

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TY - JOUR

T1 - Synthesis, structure, theoretical studies and electrochemistry of Ru(II)–N heterocyclic carbenes

AU - Maity, Lakshmikanta

AU - Das Adhikary, Sirsendu

AU - Mondal, Ambarish

AU - Kisan, Hemanta K.

AU - Isab, Anvarhusein A.

AU - Goswami, Shyamaprosad

AU - Dinda, Joydev

PY - 2018/7/1

Y1 - 2018/7/1

N2 - Synthesis, structure, electrochemistry and theoretical studies of Ru(II) complexes, 1-(2-Pyrimidyl)-3-(methyl) imidazoline-2-ylidene tetraacetonitrileruthenium(II)hexafluorophosphate, 2 and 1-(2-Pyrimidyl)-3-(methyl)benzimidazoline-2-ylidene tetraacetonitrileruthenium(II)hexafluorophosphate, 4 bearing pyrimidine functionalized C,N donor N-heterocyclic carbene proligands 1-(2-Pyrimidyl)-3-(methyl)imidazolium hexafluorophosphate; 1-H(PF6) and 1-(2-Pyrimidyl)-3-(methyl)benzimidazolium hexafluorophosphate; 3-H(PF6) have been reported. The compounds were fully characterized by elemental analysis, NMR, UV–Vis spectroscopy and finally the solid state structure of 2 is confirmed by X-ray diffraction studies. Theoretically geometry of complex 4 is optimized using B3LYP-D3/def2-TZVP. Natural Bond Orbital (NBO) analysis of complexes 2 and 4 support the π-back bonding Ru → N[dbnd]Ccarbene. Cyclic voltammetry studies revealed Ru(II)/Ru(III) reversible oxidation couple at 0.50 and 0.52 eV respectively for complexes 2 and 4; the higher oxidation potential of 4 compared to 2 is assigned due to π-acid character of benzimidazole.

AB - Synthesis, structure, electrochemistry and theoretical studies of Ru(II) complexes, 1-(2-Pyrimidyl)-3-(methyl) imidazoline-2-ylidene tetraacetonitrileruthenium(II)hexafluorophosphate, 2 and 1-(2-Pyrimidyl)-3-(methyl)benzimidazoline-2-ylidene tetraacetonitrileruthenium(II)hexafluorophosphate, 4 bearing pyrimidine functionalized C,N donor N-heterocyclic carbene proligands 1-(2-Pyrimidyl)-3-(methyl)imidazolium hexafluorophosphate; 1-H(PF6) and 1-(2-Pyrimidyl)-3-(methyl)benzimidazolium hexafluorophosphate; 3-H(PF6) have been reported. The compounds were fully characterized by elemental analysis, NMR, UV–Vis spectroscopy and finally the solid state structure of 2 is confirmed by X-ray diffraction studies. Theoretically geometry of complex 4 is optimized using B3LYP-D3/def2-TZVP. Natural Bond Orbital (NBO) analysis of complexes 2 and 4 support the π-back bonding Ru → N[dbnd]Ccarbene. Cyclic voltammetry studies revealed Ru(II)/Ru(III) reversible oxidation couple at 0.50 and 0.52 eV respectively for complexes 2 and 4; the higher oxidation potential of 4 compared to 2 is assigned due to π-acid character of benzimidazole.

KW - Electrochemistry

KW - N-heterocyclic carbene

KW - Pyrimidine

KW - Ruthenium-NHC

KW - X-ray structure

UR - https://www.scopus.com/pages/publications/85046350465

U2 - 10.1016/j.ica.2018.04.029

DO - 10.1016/j.ica.2018.04.029

M3 - Article

AN - SCOPUS:85046350465

SN - 0020-1693

VL - 479

SP - 141

EP - 147

JO - Inorganica Chimica Acta

JF - Inorganica Chimica Acta

ER -

Synthesis, structure, theoretical studies and electrochemistry of Ru(II)–N heterocyclic carbenes

Abstract

Bibliographical note

Keywords

ASJC Scopus subject areas

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