Synthesis, characterization and molecular sensing capability of fac-[Re(CO)3(κ2-N,N-dpktsc)Cl] where dpktsc = di-2-pyridylketone thiosemicarbazone

Mohammed Bakir; Ordel Brown

doi:10.1016/j.molstruc.2009.04.039

Synthesis, characterization and molecular sensing capability of fac-[Re(CO)₃(κ²-N,N-dpktsc)Cl] where dpktsc = di-2-pyridylketone thiosemicarbazone

Mohammed Bakir^*, Ordel Brown

^*Corresponding author for this work

McCormick Office of Undergraduate Engineering

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

17 Scopus citations

Abstract

When di-2-pyridyl ketone thiosemicarbazone (dpktsc) was allowed to react with [Re(CO)₅Cl] in toluene under reflux, fac-[Re(CO)₃(κ²-N,N-dpktsc)Cl] was isolated in good yield. The identity of fac-[Re(CO)₃(κ²-N,N-dpktsc)Cl] was established from the results of its elemental analysis, spectroscopic, and electrochemical properties. The infrared spectra of fac-[Re(CO)₃(κ²-N,N-dpktsc)Cl] show the facial coordination of the carbonyl groups, and the pyridyl N,N-coordination of dpktsc. ¹H NMR measurements on fac-[Re(CO)₃(κ²-N,N-dpktsc)Cl] in d₆-dmso and d₆-acetone confirmed the pyridyl N,N-coordination of dpktsc, and showed strong solvent dependence as manifested by the sensitivity of thioamide and ammine protons to their surroundings. The electronic absorption spectra of fac-[Re(CO)₃(κ²-N,N-dpktsc)Cl] in protophilic solvents (dmso and dmf) display two intra-ligand charge transfer (ILCT) transitions at 476 and 360 nm and in non-protophilic solvents a single ILCT transition at 346 nm in CH₃CN and 342 nm in CH₂Cl₂. Reversible interconversion between fac-[Re(CO)₃(κ²-N,N-dpktsc)Cl] and its conjugate base was established in protophilic solvents using a base to shift the equilibrium to the conjugate base and an acid to shift the equilibrium or conjugate base to the neutral form. Substrates in concentrations as low as 1 × 10^-10 M can be detected and determined using protophilic solutions of fac-[Re(CO)₃(κ²-N,N-dpktsc)Cl]. When MCl₂ (M = Zn, Cd or Hg) was allowed to interact with fac-[Re(CO)₃(κ²-N,N-dpktsc)Cl] in protophilic solvents, the intensity of the low energy ILCT band disappeared and a shift in the high energy ILCT electronic transition was observed that hints to the coordination of MCl₂ to fac-[Re(CO)₃(κ²-N,N-dpktsc)Cl]. Electrochemical measurements on fac-[Re(CO)₃(κ²-N,N-dpktsc)Cl] in dmf showed sequential irreversible redox processes in accord with the electrochemical reduction or oxidation of the thiosemicarbazone moiety.

Original language	English (US)
Pages (from-to)	65-71
Number of pages	7
Journal	Journal of Molecular Structure
Volume	930
Issue number	1-3
DOIs	https://doi.org/10.1016/j.molstruc.2009.04.039
State	Published - Jul 30 2009

Keywords

Di-2-pyridyl ketone
Electrochemistry
Rhenium
Sensors
Spectroscopy
Thiosemicarbazone metal complexes

ASJC Scopus subject areas

Analytical Chemistry
Spectroscopy
Organic Chemistry
Inorganic Chemistry

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10.1016/j.molstruc.2009.04.039

Cite this

@article{e057d4ea214e49d08b21b95572c0711c,

title = "Synthesis, characterization and molecular sensing capability of fac-[Re(CO)3(κ2-N,N-dpktsc)Cl] where dpktsc = di-2-pyridylketone thiosemicarbazone",

abstract = "When di-2-pyridyl ketone thiosemicarbazone (dpktsc) was allowed to react with [Re(CO)5Cl] in toluene under reflux, fac-[Re(CO)3(κ2-N,N-dpktsc)Cl] was isolated in good yield. The identity of fac-[Re(CO)3(κ2-N,N-dpktsc)Cl] was established from the results of its elemental analysis, spectroscopic, and electrochemical properties. The infrared spectra of fac-[Re(CO)3(κ2-N,N-dpktsc)Cl] show the facial coordination of the carbonyl groups, and the pyridyl N,N-coordination of dpktsc. 1H NMR measurements on fac-[Re(CO)3(κ2-N,N-dpktsc)Cl] in d6-dmso and d6-acetone confirmed the pyridyl N,N-coordination of dpktsc, and showed strong solvent dependence as manifested by the sensitivity of thioamide and ammine protons to their surroundings. The electronic absorption spectra of fac-[Re(CO)3(κ2-N,N-dpktsc)Cl] in protophilic solvents (dmso and dmf) display two intra-ligand charge transfer (ILCT) transitions at 476 and 360 nm and in non-protophilic solvents a single ILCT transition at 346 nm in CH3CN and 342 nm in CH2Cl2. Reversible interconversion between fac-[Re(CO)3(κ2-N,N-dpktsc)Cl] and its conjugate base was established in protophilic solvents using a base to shift the equilibrium to the conjugate base and an acid to shift the equilibrium or conjugate base to the neutral form. Substrates in concentrations as low as 1 × 10-10 M can be detected and determined using protophilic solutions of fac-[Re(CO)3(κ2-N,N-dpktsc)Cl]. When MCl2 (M = Zn, Cd or Hg) was allowed to interact with fac-[Re(CO)3(κ2-N,N-dpktsc)Cl] in protophilic solvents, the intensity of the low energy ILCT band disappeared and a shift in the high energy ILCT electronic transition was observed that hints to the coordination of MCl2 to fac-[Re(CO)3(κ2-N,N-dpktsc)Cl]. Electrochemical measurements on fac-[Re(CO)3(κ2-N,N-dpktsc)Cl] in dmf showed sequential irreversible redox processes in accord with the electrochemical reduction or oxidation of the thiosemicarbazone moiety.",

keywords = "Di-2-pyridyl ketone, Electrochemistry, Rhenium, Sensors, Spectroscopy, Thiosemicarbazone metal complexes",

author = "Mohammed Bakir and Ordel Brown",

year = "2009",

month = jul,

day = "30",

doi = "10.1016/j.molstruc.2009.04.039",

language = "English (US)",

volume = "930",

pages = "65--71",

journal = "Journal of Molecular Structure",

issn = "0022-2860",

publisher = "Elsevier B.V.",

number = "1-3",

}

TY - JOUR

T1 - Synthesis, characterization and molecular sensing capability of fac-[Re(CO)3(κ2-N,N-dpktsc)Cl] where dpktsc = di-2-pyridylketone thiosemicarbazone

AU - Bakir, Mohammed

AU - Brown, Ordel

PY - 2009/7/30

Y1 - 2009/7/30

N2 - When di-2-pyridyl ketone thiosemicarbazone (dpktsc) was allowed to react with [Re(CO)5Cl] in toluene under reflux, fac-[Re(CO)3(κ2-N,N-dpktsc)Cl] was isolated in good yield. The identity of fac-[Re(CO)3(κ2-N,N-dpktsc)Cl] was established from the results of its elemental analysis, spectroscopic, and electrochemical properties. The infrared spectra of fac-[Re(CO)3(κ2-N,N-dpktsc)Cl] show the facial coordination of the carbonyl groups, and the pyridyl N,N-coordination of dpktsc. 1H NMR measurements on fac-[Re(CO)3(κ2-N,N-dpktsc)Cl] in d6-dmso and d6-acetone confirmed the pyridyl N,N-coordination of dpktsc, and showed strong solvent dependence as manifested by the sensitivity of thioamide and ammine protons to their surroundings. The electronic absorption spectra of fac-[Re(CO)3(κ2-N,N-dpktsc)Cl] in protophilic solvents (dmso and dmf) display two intra-ligand charge transfer (ILCT) transitions at 476 and 360 nm and in non-protophilic solvents a single ILCT transition at 346 nm in CH3CN and 342 nm in CH2Cl2. Reversible interconversion between fac-[Re(CO)3(κ2-N,N-dpktsc)Cl] and its conjugate base was established in protophilic solvents using a base to shift the equilibrium to the conjugate base and an acid to shift the equilibrium or conjugate base to the neutral form. Substrates in concentrations as low as 1 × 10-10 M can be detected and determined using protophilic solutions of fac-[Re(CO)3(κ2-N,N-dpktsc)Cl]. When MCl2 (M = Zn, Cd or Hg) was allowed to interact with fac-[Re(CO)3(κ2-N,N-dpktsc)Cl] in protophilic solvents, the intensity of the low energy ILCT band disappeared and a shift in the high energy ILCT electronic transition was observed that hints to the coordination of MCl2 to fac-[Re(CO)3(κ2-N,N-dpktsc)Cl]. Electrochemical measurements on fac-[Re(CO)3(κ2-N,N-dpktsc)Cl] in dmf showed sequential irreversible redox processes in accord with the electrochemical reduction or oxidation of the thiosemicarbazone moiety.

AB - When di-2-pyridyl ketone thiosemicarbazone (dpktsc) was allowed to react with [Re(CO)5Cl] in toluene under reflux, fac-[Re(CO)3(κ2-N,N-dpktsc)Cl] was isolated in good yield. The identity of fac-[Re(CO)3(κ2-N,N-dpktsc)Cl] was established from the results of its elemental analysis, spectroscopic, and electrochemical properties. The infrared spectra of fac-[Re(CO)3(κ2-N,N-dpktsc)Cl] show the facial coordination of the carbonyl groups, and the pyridyl N,N-coordination of dpktsc. 1H NMR measurements on fac-[Re(CO)3(κ2-N,N-dpktsc)Cl] in d6-dmso and d6-acetone confirmed the pyridyl N,N-coordination of dpktsc, and showed strong solvent dependence as manifested by the sensitivity of thioamide and ammine protons to their surroundings. The electronic absorption spectra of fac-[Re(CO)3(κ2-N,N-dpktsc)Cl] in protophilic solvents (dmso and dmf) display two intra-ligand charge transfer (ILCT) transitions at 476 and 360 nm and in non-protophilic solvents a single ILCT transition at 346 nm in CH3CN and 342 nm in CH2Cl2. Reversible interconversion between fac-[Re(CO)3(κ2-N,N-dpktsc)Cl] and its conjugate base was established in protophilic solvents using a base to shift the equilibrium to the conjugate base and an acid to shift the equilibrium or conjugate base to the neutral form. Substrates in concentrations as low as 1 × 10-10 M can be detected and determined using protophilic solutions of fac-[Re(CO)3(κ2-N,N-dpktsc)Cl]. When MCl2 (M = Zn, Cd or Hg) was allowed to interact with fac-[Re(CO)3(κ2-N,N-dpktsc)Cl] in protophilic solvents, the intensity of the low energy ILCT band disappeared and a shift in the high energy ILCT electronic transition was observed that hints to the coordination of MCl2 to fac-[Re(CO)3(κ2-N,N-dpktsc)Cl]. Electrochemical measurements on fac-[Re(CO)3(κ2-N,N-dpktsc)Cl] in dmf showed sequential irreversible redox processes in accord with the electrochemical reduction or oxidation of the thiosemicarbazone moiety.

KW - Di-2-pyridyl ketone

KW - Electrochemistry

KW - Rhenium

KW - Sensors

KW - Spectroscopy

KW - Thiosemicarbazone metal complexes

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