A new method to radical anions derived from s-Indacene organobimetallic complexes, their ESR characterization

D. MacLeod Carey; C. Adams; A. Muñoz-Castro; C. Morales-Verdejo; J. F. Araneda; I. Chavez; J. M. Manríquez; A. Castel; P. Rivière; M. Rivière-Baudet; D. Matioszek; R. Septelean; I. Martinez; R. Arratia-Pérez

doi:10.1016/j.ica.2012.05.033

A new method to radical anions derived from s-Indacene organobimetallic complexes, their ESR characterization

D. MacLeod Carey, C. Adams, A. Muñoz-Castro, C. Morales-Verdejo, J. F. Araneda, I. Chavez, J. M. Manríquez, A. Castel, P. Rivière, M. Rivière-Baudet, D. Matioszek, R. Septelean, I. Martinez, R. Arratia-Pérez

Facultad Ciencias Exactas

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6 Citas (Scopus)

Resumen

The following organobimetallic radical anions derived from 2,6-diethyl-4,8-dimethyl-s-indacene (s-Ic′): [CODRh(s-Ic′)RhCOD] ^- (IIa), [Cp^*Ru(s-Ic′)RuCp^*] ^- (IIb), [Cp^*Ru(s-Ic′)RhCOD] ^- (IIc), [Cp^*Ru(s-Ic′)NiCp^*]^- (IId) [(CO)₃Mn(s-Ic′)NiCp^*]^- (IIe) and [Cp^*Fe(s-Ic′)NiCp^*]^- (IIf) (COD = 1,5-cyclooctadiene; Cp^* = pentamethylcyclopentadienyl) were prepared by reduction of the parent complexes using a monoelectronic transfer from an electron rich olefin. The radical anions were fully characterized by ESR spectroscopy which usually gave a well resolved hyperfine coupling structure, indicating that the spin distribution in the symmetrical radical anions (IIa, IIb) affects mainly the organic spacer whereas in the unsymmetrical ones (IIc-f) it is displaced towards the most electronegative metal center and its ligands. This effect is most pronounced in IId, IIe and IIf. The calculated g tensor values of the radical anions are in good agreement with the experimental values. In heterobimetallic radical anions, the dissymmetric spin distribution shows that the two metals present different electrophile properties leading to potentially different catalytic activities.

Idioma original	Inglés
Páginas (desde-hasta)	154-159
Número de páginas	6
Publicación	Inorganica Chimica Acta
Volumen	392
DOI	https://doi.org/10.1016/j.ica.2012.05.033
Estado	Publicada - 30 sep. 2012

Áreas temáticas de ASJC Scopus

Química física y teórica
Química inorgánica
Química de los materiales

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10.1016/j.ica.2012.05.033

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MacLeod Carey, D., Adams, C., Muñoz-Castro, A., Morales-Verdejo, C., Araneda, J. F., Chavez, I., Manríquez, J. M., Castel, A., Rivière, P., Rivière-Baudet, M., Matioszek, D., Septelean, R., Martinez, I., & Arratia-Pérez, R. (2012). A new method to radical anions derived from s-Indacene organobimetallic complexes, their ESR characterization. Inorganica Chimica Acta, 392, 154-159. https://doi.org/10.1016/j.ica.2012.05.033

@article{b314f2ab5fbf420891e5df8444d4a44f,

title = "A new method to radical anions derived from s-Indacene organobimetallic complexes, their ESR characterization",

abstract = "The following organobimetallic radical anions derived from 2,6-diethyl-4,8-dimethyl-s-indacene (s-Ic′): [CODRh(s-Ic′)RhCOD] - (IIa), [Cp*Ru(s-Ic′)RuCp*] - (IIb), [Cp*Ru(s-Ic′)RhCOD] - (IIc), [Cp*Ru(s-Ic′)NiCp*]- (IId) [(CO)3Mn(s-Ic′)NiCp*]- (IIe) and [Cp*Fe(s-Ic′)NiCp*]- (IIf) (COD = 1,5-cyclooctadiene; Cp* = pentamethylcyclopentadienyl) were prepared by reduction of the parent complexes using a monoelectronic transfer from an electron rich olefin. The radical anions were fully characterized by ESR spectroscopy which usually gave a well resolved hyperfine coupling structure, indicating that the spin distribution in the symmetrical radical anions (IIa, IIb) affects mainly the organic spacer whereas in the unsymmetrical ones (IIc-f) it is displaced towards the most electronegative metal center and its ligands. This effect is most pronounced in IId, IIe and IIf. The calculated g tensor values of the radical anions are in good agreement with the experimental values. In heterobimetallic radical anions, the dissymmetric spin distribution shows that the two metals present different electrophile properties leading to potentially different catalytic activities.",

keywords = "DFT, ESR, Radical anions, s-Indacene",

author = "{MacLeod Carey}, D. and C. Adams and A. Mu{\~n}oz-Castro and C. Morales-Verdejo and Araneda, {J. F.} and I. Chavez and Manr{\'i}quez, {J. M.} and A. Castel and P. Rivi{\`e}re and M. Rivi{\`e}re-Baudet and D. Matioszek and R. Septelean and I. Martinez and R. Arratia-P{\'e}rez",

year = "2012",

month = sep,

day = "30",

doi = "10.1016/j.ica.2012.05.033",

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journal = "Inorganica Chimica Acta",

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MacLeod Carey, D, Adams, C, Muñoz-Castro, A, Morales-Verdejo, C, Araneda, JF, Chavez, I, Manríquez, JM, Castel, A, Rivière, P, Rivière-Baudet, M, Matioszek, D, Septelean, R, Martinez, I & Arratia-Pérez, R 2012, 'A new method to radical anions derived from s-Indacene organobimetallic complexes, their ESR characterization', Inorganica Chimica Acta, vol. 392, pp. 154-159. https://doi.org/10.1016/j.ica.2012.05.033

TY - JOUR

T1 - A new method to radical anions derived from s-Indacene organobimetallic complexes, their ESR characterization

AU - MacLeod Carey, D.

AU - Adams, C.

AU - Muñoz-Castro, A.

AU - Morales-Verdejo, C.

AU - Araneda, J. F.

AU - Chavez, I.

AU - Manríquez, J. M.

AU - Castel, A.

AU - Rivière, P.

AU - Rivière-Baudet, M.

AU - Matioszek, D.

AU - Septelean, R.

AU - Martinez, I.

AU - Arratia-Pérez, R.

PY - 2012/9/30

Y1 - 2012/9/30

N2 - The following organobimetallic radical anions derived from 2,6-diethyl-4,8-dimethyl-s-indacene (s-Ic′): [CODRh(s-Ic′)RhCOD] - (IIa), [Cp*Ru(s-Ic′)RuCp*] - (IIb), [Cp*Ru(s-Ic′)RhCOD] - (IIc), [Cp*Ru(s-Ic′)NiCp*]- (IId) [(CO)3Mn(s-Ic′)NiCp*]- (IIe) and [Cp*Fe(s-Ic′)NiCp*]- (IIf) (COD = 1,5-cyclooctadiene; Cp* = pentamethylcyclopentadienyl) were prepared by reduction of the parent complexes using a monoelectronic transfer from an electron rich olefin. The radical anions were fully characterized by ESR spectroscopy which usually gave a well resolved hyperfine coupling structure, indicating that the spin distribution in the symmetrical radical anions (IIa, IIb) affects mainly the organic spacer whereas in the unsymmetrical ones (IIc-f) it is displaced towards the most electronegative metal center and its ligands. This effect is most pronounced in IId, IIe and IIf. The calculated g tensor values of the radical anions are in good agreement with the experimental values. In heterobimetallic radical anions, the dissymmetric spin distribution shows that the two metals present different electrophile properties leading to potentially different catalytic activities.

AB - The following organobimetallic radical anions derived from 2,6-diethyl-4,8-dimethyl-s-indacene (s-Ic′): [CODRh(s-Ic′)RhCOD] - (IIa), [Cp*Ru(s-Ic′)RuCp*] - (IIb), [Cp*Ru(s-Ic′)RhCOD] - (IIc), [Cp*Ru(s-Ic′)NiCp*]- (IId) [(CO)3Mn(s-Ic′)NiCp*]- (IIe) and [Cp*Fe(s-Ic′)NiCp*]- (IIf) (COD = 1,5-cyclooctadiene; Cp* = pentamethylcyclopentadienyl) were prepared by reduction of the parent complexes using a monoelectronic transfer from an electron rich olefin. The radical anions were fully characterized by ESR spectroscopy which usually gave a well resolved hyperfine coupling structure, indicating that the spin distribution in the symmetrical radical anions (IIa, IIb) affects mainly the organic spacer whereas in the unsymmetrical ones (IIc-f) it is displaced towards the most electronegative metal center and its ligands. This effect is most pronounced in IId, IIe and IIf. The calculated g tensor values of the radical anions are in good agreement with the experimental values. In heterobimetallic radical anions, the dissymmetric spin distribution shows that the two metals present different electrophile properties leading to potentially different catalytic activities.

KW - DFT

KW - ESR

KW - Radical anions

KW - s-Indacene

UR - http://www.scopus.com/inward/record.url?scp=84865741844&partnerID=8YFLogxK

U2 - 10.1016/j.ica.2012.05.033

DO - 10.1016/j.ica.2012.05.033

M3 - Article

AN - SCOPUS:84865741844

SN - 0020-1693

VL - 392

SP - 154

EP - 159

JO - Inorganica Chimica Acta

JF - Inorganica Chimica Acta

ER -

A new method to radical anions derived from s-Indacene organobimetallic complexes, their ESR characterization

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