Electrochemistry of acetate-, carbonate-, sulfate-, and dihydrogenphosphate-bridged dirhodium(II) complexes

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Date

2003

Authors

Özalp Yaman, Şeniz
Yaman,Ş.Ö.
Önal,A.M.
Isci,H.

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Publisher

Verlag der Zeitschrift fur Naturforschung

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Chemical Engineering
(2010)
Established in 2010, and aiming to train the students with the capacity to meet the demands of the 21st Century, the Chemical Engineering Department provides a sound chemistry background through intense coursework and laboratory practices, along with fundamental courses such as Physics and Mathematics within the freshman and sophomore years, following preparatory English courses.In the final two years of the program, engineering courses are offered with laboratory practice and state-of-the-art simulation programs, combining theory with practice.

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Abstract

Complexes, [Rh2(B-B)4L2]n (B-B = CH3CO2-, L = CH3CN, H2O, Cl-, Br-, SCN-; B-B = CO32-, SO42-, H2PO4-, L = H2O, Cl-, Br-, SCN-) were prepared and their cyclic voltammograms (CV) and electronic absorption spectra were measured in solution. The CV of the complexes exhibits a reversible one-electron transfer from a metal-based orbital. Constant potential electrolysis at the oxidation peak potential of [Rh2 (O2CCH3)4 (NCCH3)2] in acetonitrile yielded [Rh2 (O2CCH3)4 (NCCH3)2]+, a mixed valent Rh(II)-Rh(III) cation complex. The formation of the mixed valent complex was monitored by measuring electronic absorption spectra of the solution in situ during the oxidative electrolysis. The reductive electrolysis of the mixed valent complex solution, in the same electrolysis cell, yielded the original electronic absorption spectrum of the starting complex. The changes in the oxidation and reduction potentials of the complexes with different axial ligands, L = H2O, Cl-, Br-, SCN-, are correlated to the relative energy changes of HOMO and LUMO of the complexes, which indicates the metal-axial ligand σ- and π-bonding interactions. Spectroscopic and CV data indicate that the degree of σ-interaction is Cl- > Br- > SCN-, and that of π-interaction is Br- > SCN- > Cl-.

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Keywords

Cyclic Voltammetry, Dirhodium(II) Complexes, Spectroelectrochemistry

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Fields of Science

Citation

2

WoS Q

Q4

Scopus Q

Q3

Source

Zeitschrift fur Naturforschung - Section B Journal of Chemical Sciences

Volume

58

Issue

6

Start Page

563

End Page

570

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