ESR investigation of the substitution reactions in rhodium(I) complexes with spin-labeled ligands

Nevodchikov, V. I.; Abakumov, G. A.; Cherkasov, V. K.; Razuvaev, G. A.

doi:10.1016/s0022-328x(00)85964-1

Cited by 48 publications

(31 citation statements)

References 7 publications

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“…One of the mostly interesting our papers was dedicated to carbonyl-osemiquinonato complexes of rhodium [2]. In some cases the nature of o-semiquinone used as spin label has some significance [4].…”

Section: Resultsmentioning

confidence: 99%

o-Semiquinonato and o-iminosemiquinonato rhodium complexes. EPR study of the reactions in coordination sphere of rhodium

Bubnov

Teplova

Kozhanov

et al. 2011

Journal of Magnetic Resonance

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Section: Resultsmentioning

confidence: 99%

o-Semiquinonato and o-iminosemiquinonato rhodium complexes. EPR study of the reactions in coordination sphere of rhodium

Bubnov

Teplova

Kozhanov

et al. 2011

Journal of Magnetic Resonance

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“…The low HFC constants with the phosphorus magnetic nuclei (0.255-0.257 mT) in the diphosphine ligand attest to a square planar geometry of the resulting cations. 7, 8 The CV (i(E)) and CV-ESR (s´(E)) curves for com pound 1 are shown in Fig. 2, a.…”

Section: Resultsmentioning

confidence: 99%

Study of electrochemical oxidation of nickel catecholate complexes with bis(diphenylphosphino)ethane by cyclic voltammetry and ESR

et al. 2007

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One and two electron electrochemical oxidation of the (dppe)Ni(Cat) complexes (dppe is bis(diphenylphosphino)ethane, Cat is the sterically hindered catechol dianion) was studied. The transfer of the first electron proceeds reversibly to give paramagnetic species; parameters of their EPR spectra attest to a square planar geometry of one electron oxidation products. The transfer of the second electron is irreversible because of co proportionation of radical cations involving the initial complexes and the generated dications.In recent years, metal coordination compounds with paramagnetic ligands, including о semiquinone ligands, have attracted considerable attention of researchers. The molecules of these compounds can contain several para magnetic centers of various nature, whose sign and energy of exchange interactions are determined by the electronic structure and geometric features. 1-3 Paramagnetic ligands are often electrochemically active; the electrochemical reduction or oxidation of complexes may involve not only transformations of the central metal ion but also ligand transformations, which change the magnetic properties of the ligands and the system as a whole.By combining electrochemical methods with ESR spectroscopy, one can gain additional information about the electrode processes, electronic structure, geometry, and reactivity of depolarizers. In some cases, using the ESR spectrum of a paramagnetic substrate, one can iden tify the localization region of the unpaired electron and the geometry of magnetic nuclei.Methods for simultaneous recording of ESR signals and electrochemical characteristics using an electrolytic cell-ESR in a cavity of the ESR spectrometer in a potentiostatic mode, by chronopotentiomety, and cyclic voltammetry (CV) are known. 4,5 However, direct com parison of CV curves and ESR signal levels is not entirely valid, because the current is the first derivative of the charge that has passed through the cell, while the ESR signal level is proportional to the proper charge related to the depolarizer under study.Currently a new method, electron spin resonance detected voltammetry (V-ESR) is being developed. This method comprises two traditional methods, voltammetry and ESR, which are combined by an original three elec trode electrolytic ESR cell 6 (El-ESR) for investigation of paramagnetic species and a computer controlling the ESR spectrometer and the electrochemical setup consist ing of a programming device and a potentiostat. The method allows simultaneous recording of usual volt ammetric curves i(E) and also dependences of the ESR signal intensity (s(E)) and its first derivative (s´(E)) on the potential. In this work, the V-ESR technique was used to study nickel catecholate complexes 1 and 2 with bis(di phenylphosphino)ethane (dppe).

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“…More bulky iron and manganese complexes Fe(ISQ L3 ) 2 Br (27) and Mn(ISQ L2 ) 2 Cl (28) were prepared from the corresponding metal halides (FeBr 2 , MnCl 2 ), corresponding thallium o-iminobenzosemiquinones and o-iminobenzoquinone in molar ratio 1:1:1 [55].…”

Section: Synthesismentioning

confidence: 99%

“…Selected structural data on M(ISQ) 2 X and M(ISQ) 2 L types complexes are shown in Table 2 The electronic spectra of all M(ISQ) 2 X type complexes (19)(20)(21)(22)(23)(24)(25)(26)(27)(28)(29)(30)(31)(32) are characterized by a very intense broad absorption with maximum in the range 700-850 nm (with ε ∼ 0.3-1.2 × 10 4 M −1 cm −1 ) and another in the range 450-700 nm (with ε ∼ 0.8-1.5 × 10 4 M −1 cm −1 ). There have been no detailed assignment of these bands.…”

Section: Structure and Magnetismmentioning

confidence: 99%

“…The presence of nitrogen (its main isotope 14 N is magnetic) in o-iminoquinones reveals additional information on the spin density distribution in chelate ring. The application of o-iminosemiquinone (as well as o-semiquinone) as a spin label in metal complexes allows one to monitor complex composition, structure and dynamic processes simply by means of EPR spectroscopy [8,[26][27][28][29][30][31].…”

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

Transition metal complexes with bulky 4,6-di-tert-butyl-N-aryl(alkyl)-o-iminobenzoquinonato ligands: Structure, EPR and magnetism

Poddel’sky

Cherkasov

Abakumov

2009

Coordination Chemistry Reviews

319

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ESR investigation of the substitution reactions in rhodium(I) complexes with spin-labeled ligands

Cited by 48 publications

References 7 publications

o-Semiquinonato and o-iminosemiquinonato rhodium complexes. EPR study of the reactions in coordination sphere of rhodium

o-Semiquinonato and o-iminosemiquinonato rhodium complexes. EPR study of the reactions in coordination sphere of rhodium

Study of electrochemical oxidation of nickel catecholate complexes with bis(diphenylphosphino)ethane by cyclic voltammetry and ESR

Transition metal complexes with bulky 4,6-di-tert-butyl-N-aryl(alkyl)-o-iminobenzoquinonato ligands: Structure, EPR and magnetism

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