Optical, electrochemical and structural studies of the first rhenium compound of di-2-pyridylketone benzoylhydrazone (dpkbz) fac-Re(CO) 3(dpkbh)Cl

Mohammed Bakir; Ordel Brown

doi:10.1016/S0020-1693(03)00324-4

Optical, electrochemical and structural studies of the first rhenium compound of di-2-pyridylketone benzoylhydrazone (dpkbz) fac-Re(CO) ₃(dpkbh)Cl

Mohammed Bakir^*, Ordel Brown

^*Corresponding author for this work

McCormick Office of Undergraduate Engineering

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

18 Scopus citations

Abstract

The reaction between Re(CO)₅Cl and di-2-pyridylketone benzoylhydrazone (dpkbh) in refluxing toluene gave fac-Re(CO) ₃(dpkbh)Cl in good yield. Spectroscopic and electrochemical measurements on fac-Re(CO)₃(dpkbh)Cl revealed strong solvent-solute interaction, as manifested by the sensitivity of its reduction potentials and electronic absorption spectra to solvent variations. Spectroscopic and thermo-optical measurements in polar solvents in the presence of NaBH ₄ and NaBF_4, or NaOH and citric acid reveal reversible interconversion between the low- and high-energy electronic states of fac-Re(CO)₃(dpkbh)Cl at 440 and 318 nm. Electrochemical measurements on fac-Re(CO)₃(dpkbh)Cl show irreversible redox processes pointing to electrochemical transformations following the first electronic transfer(s). Crystals of fac-Re(CO)₃(dpkbh)Cl obtained from an acetonitrile solution of fac-Re(CO)₃(dpkbh)Cl are centric and crystals of fac-Re(CO)₃(dpkbh)Cl·dmso obtained from a dmso solutions of fac-Re(CO)₃(dpkbh)Cl are acentric. Structural studies show non-identical twins of fac-Re(CO)₃(dpkbh)Cl and fac-Re(CO) ₃(dpkbh)Cl·dmso with distorted octahedral coordination about rhenium and the conformation about the amide group is syn- in fac-Re(CO) ₃(dpkbh)Cl and anti- in fac-Re(CO)₃(dpkbh)Cl·dmso. The packing of molecules shows a web of hydrogen bonds that may account for the stability of different conformations observed in the solid state.

Original language	English (US)
Pages (from-to)	89-98
Number of pages	10
Journal	Inorganica Chimica Acta
Volume	353
DOIs	https://doi.org/10.1016/S0020-1693(03)00324-4
State	Published - Sep 8 2003

Keywords

Di-2-pyridyl ketone
Hydrazone
Optosensing
Rhenium

ASJC Scopus subject areas

Physical and Theoretical Chemistry
Inorganic Chemistry
Materials Chemistry

Access to Document

10.1016/S0020-1693(03)00324-4

Cite this

@article{9632010ce5174a8aa838e136ea1e446d,

title = "Optical, electrochemical and structural studies of the first rhenium compound of di-2-pyridylketone benzoylhydrazone (dpkbz) fac-Re(CO) 3(dpkbh)Cl",

abstract = "The reaction between Re(CO)5Cl and di-2-pyridylketone benzoylhydrazone (dpkbh) in refluxing toluene gave fac-Re(CO) 3(dpkbh)Cl in good yield. Spectroscopic and electrochemical measurements on fac-Re(CO)3(dpkbh)Cl revealed strong solvent-solute interaction, as manifested by the sensitivity of its reduction potentials and electronic absorption spectra to solvent variations. Spectroscopic and thermo-optical measurements in polar solvents in the presence of NaBH 4 and NaBF4, or NaOH and citric acid reveal reversible interconversion between the low- and high-energy electronic states of fac-Re(CO)3(dpkbh)Cl at 440 and 318 nm. Electrochemical measurements on fac-Re(CO)3(dpkbh)Cl show irreversible redox processes pointing to electrochemical transformations following the first electronic transfer(s). Crystals of fac-Re(CO)3(dpkbh)Cl obtained from an acetonitrile solution of fac-Re(CO)3(dpkbh)Cl are centric and crystals of fac-Re(CO)3(dpkbh)Cl·dmso obtained from a dmso solutions of fac-Re(CO)3(dpkbh)Cl are acentric. Structural studies show non-identical twins of fac-Re(CO)3(dpkbh)Cl and fac-Re(CO) 3(dpkbh)Cl·dmso with distorted octahedral coordination about rhenium and the conformation about the amide group is syn- in fac-Re(CO) 3(dpkbh)Cl and anti- in fac-Re(CO)3(dpkbh)Cl·dmso. The packing of molecules shows a web of hydrogen bonds that may account for the stability of different conformations observed in the solid state.",

keywords = "Di-2-pyridyl ketone, Hydrazone, Optosensing, Rhenium",

author = "Mohammed Bakir and Ordel Brown",

note = "Funding Information: I acknowledge funding from The University of the West Indies (UWI) and Inter-America Development Bank (IDB) for funds to establish the X-ray Laboratory at UWI-Mona.",

year = "2003",

month = sep,

day = "8",

doi = "10.1016/S0020-1693(03)00324-4",

language = "English (US)",

volume = "353",

pages = "89--98",

journal = "Inorganica Chimica Acta",

issn = "0020-1693",

publisher = "Elsevier BV",

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TY - JOUR

T1 - Optical, electrochemical and structural studies of the first rhenium compound of di-2-pyridylketone benzoylhydrazone (dpkbz) fac-Re(CO) 3(dpkbh)Cl

AU - Bakir, Mohammed

AU - Brown, Ordel

N1 - Funding Information: I acknowledge funding from The University of the West Indies (UWI) and Inter-America Development Bank (IDB) for funds to establish the X-ray Laboratory at UWI-Mona.

PY - 2003/9/8

Y1 - 2003/9/8

N2 - The reaction between Re(CO)5Cl and di-2-pyridylketone benzoylhydrazone (dpkbh) in refluxing toluene gave fac-Re(CO) 3(dpkbh)Cl in good yield. Spectroscopic and electrochemical measurements on fac-Re(CO)3(dpkbh)Cl revealed strong solvent-solute interaction, as manifested by the sensitivity of its reduction potentials and electronic absorption spectra to solvent variations. Spectroscopic and thermo-optical measurements in polar solvents in the presence of NaBH 4 and NaBF4, or NaOH and citric acid reveal reversible interconversion between the low- and high-energy electronic states of fac-Re(CO)3(dpkbh)Cl at 440 and 318 nm. Electrochemical measurements on fac-Re(CO)3(dpkbh)Cl show irreversible redox processes pointing to electrochemical transformations following the first electronic transfer(s). Crystals of fac-Re(CO)3(dpkbh)Cl obtained from an acetonitrile solution of fac-Re(CO)3(dpkbh)Cl are centric and crystals of fac-Re(CO)3(dpkbh)Cl·dmso obtained from a dmso solutions of fac-Re(CO)3(dpkbh)Cl are acentric. Structural studies show non-identical twins of fac-Re(CO)3(dpkbh)Cl and fac-Re(CO) 3(dpkbh)Cl·dmso with distorted octahedral coordination about rhenium and the conformation about the amide group is syn- in fac-Re(CO) 3(dpkbh)Cl and anti- in fac-Re(CO)3(dpkbh)Cl·dmso. The packing of molecules shows a web of hydrogen bonds that may account for the stability of different conformations observed in the solid state.

AB - The reaction between Re(CO)5Cl and di-2-pyridylketone benzoylhydrazone (dpkbh) in refluxing toluene gave fac-Re(CO) 3(dpkbh)Cl in good yield. Spectroscopic and electrochemical measurements on fac-Re(CO)3(dpkbh)Cl revealed strong solvent-solute interaction, as manifested by the sensitivity of its reduction potentials and electronic absorption spectra to solvent variations. Spectroscopic and thermo-optical measurements in polar solvents in the presence of NaBH 4 and NaBF4, or NaOH and citric acid reveal reversible interconversion between the low- and high-energy electronic states of fac-Re(CO)3(dpkbh)Cl at 440 and 318 nm. Electrochemical measurements on fac-Re(CO)3(dpkbh)Cl show irreversible redox processes pointing to electrochemical transformations following the first electronic transfer(s). Crystals of fac-Re(CO)3(dpkbh)Cl obtained from an acetonitrile solution of fac-Re(CO)3(dpkbh)Cl are centric and crystals of fac-Re(CO)3(dpkbh)Cl·dmso obtained from a dmso solutions of fac-Re(CO)3(dpkbh)Cl are acentric. Structural studies show non-identical twins of fac-Re(CO)3(dpkbh)Cl and fac-Re(CO) 3(dpkbh)Cl·dmso with distorted octahedral coordination about rhenium and the conformation about the amide group is syn- in fac-Re(CO) 3(dpkbh)Cl and anti- in fac-Re(CO)3(dpkbh)Cl·dmso. The packing of molecules shows a web of hydrogen bonds that may account for the stability of different conformations observed in the solid state.

KW - Di-2-pyridyl ketone

KW - Hydrazone

KW - Optosensing

KW - Rhenium

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JO - Inorganica Chimica Acta

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