[Cp*Ru(s-indacene)RuCp*] and [Cp*Ru(s-indacene)RuCp*]+: Experimental and theoretical findings concerning the electronic structure of neutral and mixed valence organometallic systems

D. Mac-Leod Carey, C. Morales-Verdejo, A. Muñoz-Castro, F. Burgos, D. Abril, C. Adams, E. Molins, O. Cador, I. Chávez, J. M. Manríquez, R. Arratia-Pérez, J. Y. Saillard

Resultado de la investigación: Article

19 Citas (Scopus)

Resumen

The reaction of 2,6-diethyl-4,8-dimethyl-s-indacenyl-dilithium (Li2Ic′) with [Cp*RuCl]4 gives the organometallic binuclear bis-pentamethylcyclopentadienyl-ruthenium-s-indacene complex, [{Cp*Ru}2Ic′] (1, Ic′ = 2,4-diethyl-4,8-dimethyl-s-indacene), in high yields. The subsequent oxidation of 1 with a ferricinium salt ([Fc]+[BF4]-) gives the mixed valence compound [{Cp*Ru}2Ic′]+[BF4]- (1+). Compound 1 was structurally characterized by X-ray crystallography, finding that both {Cp*Ru} fragments are coordinated to opposite sites of the Ic′ ligand. The structural and electronic features of 1 and 1+ have been rationalized by Density Functional Theory (DFT) calculations, which suggest that both metallic centers get closer to the Ic′ and subtle electronic reorganizations occurs when chemical oxidation takes place. Cyclic voltammetry and ESR experiments suggest a high electronic interaction between the metallic centers mediated by the Ic′ bridging ligand. Time dependent DFT (TD-DFT) calculations were carried out to understand and assign the intervalence band present in the mixed-valent specie (1+). The main achievement of this article is to feature the relationship of the experimental data with the computational results obtained with the Amsterdam Density Functional package (ADF). Both experimental and theoretical facts demonstrate that the mixed valence system (1+) is a delocalized one, and it can be classified as a Class III system according to the Robin & Day classification.

Idioma originalEnglish
Páginas (desde-hasta)1137-1143
Número de páginas7
PublicaciónPolyhedron
Volumen29
N.º3
DOI
EstadoPublished - 19 feb 2010

Huella dactilar

Organometallics
Electronic structure
Density functional theory
Ligands
electronic structure
valence
Oxidation
Ruthenium
X ray crystallography
electronics
density functional theory
Cyclic voltammetry
Paramagnetic resonance
ligands
oxidation
Salts
ruthenium
crystallography
fragments
salts

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry
  • Materials Chemistry

Citar esto

Mac-Leod Carey, D. ; Morales-Verdejo, C. ; Muñoz-Castro, A. ; Burgos, F. ; Abril, D. ; Adams, C. ; Molins, E. ; Cador, O. ; Chávez, I. ; Manríquez, J. M. ; Arratia-Pérez, R. ; Saillard, J. Y. / [Cp*Ru(s-indacene)RuCp*] and [Cp*Ru(s-indacene)RuCp*]+ : Experimental and theoretical findings concerning the electronic structure of neutral and mixed valence organometallic systems. En: Polyhedron. 2010 ; Vol. 29, N.º 3. pp. 1137-1143.
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title = "[Cp*Ru(s-indacene)RuCp*] and [Cp*Ru(s-indacene)RuCp*]+: Experimental and theoretical findings concerning the electronic structure of neutral and mixed valence organometallic systems",
abstract = "The reaction of 2,6-diethyl-4,8-dimethyl-s-indacenyl-dilithium (Li2Ic′) with [Cp*RuCl]4 gives the organometallic binuclear bis-pentamethylcyclopentadienyl-ruthenium-s-indacene complex, [{Cp*Ru}2Ic′] (1, Ic′ = 2,4-diethyl-4,8-dimethyl-s-indacene), in high yields. The subsequent oxidation of 1 with a ferricinium salt ([Fc]+[BF4]-) gives the mixed valence compound [{Cp*Ru}2Ic′]+[BF4]- (1+). Compound 1 was structurally characterized by X-ray crystallography, finding that both {Cp*Ru} fragments are coordinated to opposite sites of the Ic′ ligand. The structural and electronic features of 1 and 1+ have been rationalized by Density Functional Theory (DFT) calculations, which suggest that both metallic centers get closer to the Ic′ and subtle electronic reorganizations occurs when chemical oxidation takes place. Cyclic voltammetry and ESR experiments suggest a high electronic interaction between the metallic centers mediated by the Ic′ bridging ligand. Time dependent DFT (TD-DFT) calculations were carried out to understand and assign the intervalence band present in the mixed-valent specie (1+). The main achievement of this article is to feature the relationship of the experimental data with the computational results obtained with the Amsterdam Density Functional package (ADF). Both experimental and theoretical facts demonstrate that the mixed valence system (1+) is a delocalized one, and it can be classified as a Class III system according to the Robin & Day classification.",
keywords = "DFT, Electron transfer, Mixed valence, Organometallic, Ruthenium, s-Indacene",
author = "{Mac-Leod Carey}, D. and C. Morales-Verdejo and A. Mu{\~n}oz-Castro and F. Burgos and D. Abril and C. Adams and E. Molins and O. Cador and I. Ch{\'a}vez and Manr{\'i}quez, {J. M.} and R. Arratia-P{\'e}rez and Saillard, {J. Y.}",
year = "2010",
month = "2",
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doi = "10.1016/j.poly.2009.12.002",
language = "English",
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Mac-Leod Carey, D, Morales-Verdejo, C, Muñoz-Castro, A, Burgos, F, Abril, D, Adams, C, Molins, E, Cador, O, Chávez, I, Manríquez, JM, Arratia-Pérez, R & Saillard, JY 2010, '[Cp*Ru(s-indacene)RuCp*] and [Cp*Ru(s-indacene)RuCp*]+: Experimental and theoretical findings concerning the electronic structure of neutral and mixed valence organometallic systems', Polyhedron, vol. 29, n.º 3, pp. 1137-1143. https://doi.org/10.1016/j.poly.2009.12.002

[Cp*Ru(s-indacene)RuCp*] and [Cp*Ru(s-indacene)RuCp*]+ : Experimental and theoretical findings concerning the electronic structure of neutral and mixed valence organometallic systems. / Mac-Leod Carey, D.; Morales-Verdejo, C.; Muñoz-Castro, A.; Burgos, F.; Abril, D.; Adams, C.; Molins, E.; Cador, O.; Chávez, I.; Manríquez, J. M.; Arratia-Pérez, R.; Saillard, J. Y.

En: Polyhedron, Vol. 29, N.º 3, 19.02.2010, p. 1137-1143.

Resultado de la investigación: Article

TY - JOUR

T1 - [Cp*Ru(s-indacene)RuCp*] and [Cp*Ru(s-indacene)RuCp*]+

T2 - Experimental and theoretical findings concerning the electronic structure of neutral and mixed valence organometallic systems

AU - Mac-Leod Carey, D.

AU - Morales-Verdejo, C.

AU - Muñoz-Castro, A.

AU - Burgos, F.

AU - Abril, D.

AU - Adams, C.

AU - Molins, E.

AU - Cador, O.

AU - Chávez, I.

AU - Manríquez, J. M.

AU - Arratia-Pérez, R.

AU - Saillard, J. Y.

PY - 2010/2/19

Y1 - 2010/2/19

N2 - The reaction of 2,6-diethyl-4,8-dimethyl-s-indacenyl-dilithium (Li2Ic′) with [Cp*RuCl]4 gives the organometallic binuclear bis-pentamethylcyclopentadienyl-ruthenium-s-indacene complex, [{Cp*Ru}2Ic′] (1, Ic′ = 2,4-diethyl-4,8-dimethyl-s-indacene), in high yields. The subsequent oxidation of 1 with a ferricinium salt ([Fc]+[BF4]-) gives the mixed valence compound [{Cp*Ru}2Ic′]+[BF4]- (1+). Compound 1 was structurally characterized by X-ray crystallography, finding that both {Cp*Ru} fragments are coordinated to opposite sites of the Ic′ ligand. The structural and electronic features of 1 and 1+ have been rationalized by Density Functional Theory (DFT) calculations, which suggest that both metallic centers get closer to the Ic′ and subtle electronic reorganizations occurs when chemical oxidation takes place. Cyclic voltammetry and ESR experiments suggest a high electronic interaction between the metallic centers mediated by the Ic′ bridging ligand. Time dependent DFT (TD-DFT) calculations were carried out to understand and assign the intervalence band present in the mixed-valent specie (1+). The main achievement of this article is to feature the relationship of the experimental data with the computational results obtained with the Amsterdam Density Functional package (ADF). Both experimental and theoretical facts demonstrate that the mixed valence system (1+) is a delocalized one, and it can be classified as a Class III system according to the Robin & Day classification.

AB - The reaction of 2,6-diethyl-4,8-dimethyl-s-indacenyl-dilithium (Li2Ic′) with [Cp*RuCl]4 gives the organometallic binuclear bis-pentamethylcyclopentadienyl-ruthenium-s-indacene complex, [{Cp*Ru}2Ic′] (1, Ic′ = 2,4-diethyl-4,8-dimethyl-s-indacene), in high yields. The subsequent oxidation of 1 with a ferricinium salt ([Fc]+[BF4]-) gives the mixed valence compound [{Cp*Ru}2Ic′]+[BF4]- (1+). Compound 1 was structurally characterized by X-ray crystallography, finding that both {Cp*Ru} fragments are coordinated to opposite sites of the Ic′ ligand. The structural and electronic features of 1 and 1+ have been rationalized by Density Functional Theory (DFT) calculations, which suggest that both metallic centers get closer to the Ic′ and subtle electronic reorganizations occurs when chemical oxidation takes place. Cyclic voltammetry and ESR experiments suggest a high electronic interaction between the metallic centers mediated by the Ic′ bridging ligand. Time dependent DFT (TD-DFT) calculations were carried out to understand and assign the intervalence band present in the mixed-valent specie (1+). The main achievement of this article is to feature the relationship of the experimental data with the computational results obtained with the Amsterdam Density Functional package (ADF). Both experimental and theoretical facts demonstrate that the mixed valence system (1+) is a delocalized one, and it can be classified as a Class III system according to the Robin & Day classification.

KW - DFT

KW - Electron transfer

KW - Mixed valence

KW - Organometallic

KW - Ruthenium

KW - s-Indacene

UR - http://www.scopus.com/inward/record.url?scp=75149161569&partnerID=8YFLogxK

U2 - 10.1016/j.poly.2009.12.002

DO - 10.1016/j.poly.2009.12.002

M3 - Article

AN - SCOPUS:75149161569

VL - 29

SP - 1137

EP - 1143

JO - Polyhedron

JF - Polyhedron

SN - 0277-5387

IS - 3

ER -