Weitreichende elektronische Kopplung in unterschiedlichen Oxidationszuständen eines C<sub>4</sub>‐verknüpften Tris(β‐diketonato)ruthenium‐Dimers

Hoshino, Yoshimasa; Higuchi, Shigekazu; Fiedler, Jan; Su, Cheng‐Yong; Knödler, Axel; Schwederski, Brigitte; Sarkar, Biprajit; Hartmann, Heiko; Kaim, Wolfgang

doi:10.1002/ange.200390154

Cited by 21 publications

(14 citation statements)

References 22 publications

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“…[12] The barrier of the isomerization of 1 u to 2 u was computed to be 22.0 kcal mol À1 . [3c] confirm this interpretation, the g components at 2.35, 2.24, and 1.64 are very similar to those of mononuclear [Ru III (dpm) 3 ], dpm = dipivaloylmethanate (2,2,6,6-tetramethylheptan-3,5-dionate), [10] under the same conditions: g 1,2 = 2.27, g 3 = 1.69.…”

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confidence: 64%

Long‐Range Electronic Coupling in Various Oxidation States of a C₄‐Linked Tris(β‐diketonato)ruthenium Dimer

et al. 2003

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Despite an increasingly varied experimental data basis [1] and sophisticated theoretical approaches [2] there is still only a rudimentary understanding of which factors govern the extent of interaction between metal centers in formally symmetrical mixed-valent compounds. Such compounds can be considered as intermediates in ™degenerate∫ inner-sphere metal-to-metal electron transfer. The interplay between metal configurations, the metal±ligand interface, and the properties of the ligand bridge has to be considered. Although the mere metal±metal distance has often been used as a guideline [3] in the absence of other, less accessible parameters, it is clear from several experiments [1] that the electronic properties of the ligands mediating the metal±metal interaction may be more relevant than the metal±metal separation. However, the correlation between metal configurations and the bridge type also requires consideration, especially when using alternatives to the often studied d 5 /d 6 combination, [1, 3] familiar from prototypes, such as the Creutz±Taube ion [3a] [(H 3 N) 5 Ru-(m-pz)Ru(NH 3 ) 5 ] 5+ (pz = pyrazine) or partially oxidized biferrocenyl species. [4] Herein we describe the extraordinarily varied results for two different mixed-valent configurations that are accessible by single-electron transfer from the structurally characterized diruthenium(iii) complex 1. [5] The distinguishing feature of the ligand bridge is an unsaturated, cumulene-like, C 4 spacer which, in contrast to other C 4 -bridged dinuclear systems, [6] interacts with the metals through conventional Werner-type coordination, namely through b-diketonato chelate ligation. [5] The complex 1 could be characterized crystallographically, [7] it has an almost linear C 4 chain with localized singlebond/triple-bond alternation (Figure 1). At 13.1359(6) ä the metal±metal separation is much longer than in directly C 4connected diruthenium complexes (ca. 8.0 ä), [6] and the chelate rings are virtually perpendicular (90.98).

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confidence: 64%

Long‐Range Electronic Coupling in Various Oxidation States of a C₄‐Linked Tris(β‐diketonato)ruthenium Dimer

et al. 2003

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“…[37] The unusual IR features were attributed to cumulene-type resonance contributions. [37] The Ru .…”

Section: Mixed-valent Complexesmentioning

confidence: 98%

“…[37] The unusual IR features were attributed to cumulene-type resonance contributions. [37] The Ru . [38] Combinations involving oxidation states lower than the classical + III/ + II combination, such as ruthenium(I), [39] typically require stabilization through organometallic pacceptor ligands.…”

Section: Mixed-valent Complexesmentioning

confidence: 99%

“…[27,[34][35][36][37] The higher oxidation states + III and + IV imply an increased covalency of the metal-donor bond which limits the usefulness of the valence description. Frequently, the donor bridges involved are thus "non-innocent" so that alternatives according to the resonance formulation [Eq.…”

Section: Involvement Of Unusual Oxidation Statesmentioning

confidence: 99%

“…Two such examples [36,37] ) does not only cause the emergence of an intense near-infrared band at 1730 nm but also a shift to lower energy and strong increase in the intensity of the IR stretching band of the C 4 backbone. [37] The unusual IR features were attributed to cumulene-type resonance contributions.…”

Section: Mixed-valent Complexesmentioning

confidence: 99%

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Unconventional Mixed‐Valent Complexes of Ruthenium and Osmium

2007

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Recent developments have helped to extend the repertoire of mixed-valent ruthenium and osmium complexes beyond conventional systems. This extension has been achieved by using sophisticated ligands and by creating more variegated coordination patterns. The strategies employed include the use of multidentate ligands (which give rise to multinuclear and chelate complexes) and the use several redox active components (non-innocent ligands and oxidation-state ambivalence). The results offer enhanced chemical insight into metal-ligand electron-transfer situations and suggest that mixed-valent materials may eventually be exploited in molecular electronics and molecular computing.

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Unkonventionelle gemischtvalente Komplexe des Rutheniums und Osmiums

2007

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In den letzten Jahren ist es gelungen, das Repertoire gemischtvalenter Ruthenium‐ und Osmiumkomplexe über konventionelle Systeme hinaus zu erweitern, indem anspruchsvollere Liganden eingesetzt und vielgestaltigere Koordinationssituationen herbeigeführt wurden. Zu den angewendeten Strategien zählen sowohl die Nutzung mehrzähniger Liganden (die zu mehrkernigen Komplexen und Chelatkomplexen führen) als auch der Einsatz einer oder mehrerer selbst redoxaktiver Komponenten (“nicht‐unschuldige” Liganden; Stichwort: Oxidationsstufenambivalenz). Diese Untersuchungen geben tiefere Einblicke in die Abläufe von Elektronentransfers zwischen Metallen und Liganden. Gemischtvalente Materialien können in der molekularen Elektronik und im “molecular computing” Anwendung finden.

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Weitreichende elektronische Kopplung in unterschiedlichen Oxidationszuständen eines C₄‐verknüpften Tris(β‐diketonato)ruthenium‐Dimers

Cited by 21 publications

References 22 publications

Long‐Range Electronic Coupling in Various Oxidation States of a C₄‐Linked Tris(β‐diketonato)ruthenium Dimer

Long‐Range Electronic Coupling in Various Oxidation States of a C₄‐Linked Tris(β‐diketonato)ruthenium Dimer

Unconventional Mixed‐Valent Complexes of Ruthenium and Osmium

Unkonventionelle gemischtvalente Komplexe des Rutheniums und Osmiums

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Weitreichende elektronische Kopplung in unterschiedlichen Oxidationszuständen eines C4‐verknüpften Tris(β‐diketonato)ruthenium‐Dimers

Cited by 21 publications

References 22 publications

Long‐Range Electronic Coupling in Various Oxidation States of a C4‐Linked Tris(β‐diketonato)ruthenium Dimer

Long‐Range Electronic Coupling in Various Oxidation States of a C4‐Linked Tris(β‐diketonato)ruthenium Dimer

Unconventional Mixed‐Valent Complexes of Ruthenium and Osmium

Unkonventionelle gemischtvalente Komplexe des Rutheniums und Osmiums

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Weitreichende elektronische Kopplung in unterschiedlichen Oxidationszuständen eines C₄‐verknüpften Tris(β‐diketonato)ruthenium‐Dimers

Long‐Range Electronic Coupling in Various Oxidation States of a C₄‐Linked Tris(β‐diketonato)ruthenium Dimer

Long‐Range Electronic Coupling in Various Oxidation States of a C₄‐Linked Tris(β‐diketonato)ruthenium Dimer