A Cyclic Hexanuclear Heterometalladithiolene Cluster [{(Cp*Rh)2Mo(μ‐CO)2(CO)}2(S2C6H2S2)2] with Two π‐Conjugated S2C6S2 Bridges: Synthesis, Crystal Structure, and Properties

Zhu, Bilan; Shibata, Yusuke; Muratsugu, Satoshi; Yamanoi, Yoshinori; Nishihara, Hiroshi

doi:10.1002/ange.200900509

Cited by 5 publications

(6 citation statements)

References 23 publications

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“…While numerous studies of transition-metal complexes containing 1,2,4,5-tetrathiobenzene-based bridging ligands with Fe, 11 Ni II , 12 Pt II , 12b,c Rh III , 13 Ir III , 13 Ti IV , 14 Zr IV , 14 Hf IV , 14 and Ru II12c have been reported, to our knowledge, a radical form of this ligand has been isolated only once, in a Ni II 2 complex. 12b Moreover, a benzene tetrathiolate radical has not yet been investigated in the presence of paramagnetic metal centers nor has the magnetic exchange coupling been determined.…”

Section: ■ Introductionmentioning

confidence: 87%

Thiosemiquinoid Radical-Bridged Cr^III₂ Complexes with Strong Magnetic Exchange Coupling

2019

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Semiquinoid radical bridging ligands are capable of mediating exceptionally strong magnetic coupling between spin centers, a requirement for the design of high-temperature magnetic materials. We demonstrate the ability of sulfur donors to provide much stronger coupling relative to their oxygen congeners in a series of dinuclear complexes. Employing a series of chalcogen donor-based bis(bidentate) benzoquinoid bridging ligands, the series of complexes [(TPyA) 2 Cr 2 ( R L 4− )] 2+ ( O LH 4 = 1,2,4,5-tetrahydroxybenzene, OS LH 4 = 1,2-dithio-4,5-dihydroxybenzene, S LH 4 = 1,2,4,5-tetrathiobenzene, TPyA = tris(2pyridylmethyl)amine) was synthesized. Variable-temperature dc magnetic susceptibility data reveal the presence of weak antiferromagnetic superexchange coupling between Cr III centers in these complexes, with exchange constants of J = −2.83(3) ( O L 4− ), −2.28(5) ( OS L 4− ), and −1.80(2) ( S L 4− ) cm −1 . Guided by cyclic voltammetry and spectroelectrochemical measurements, chemical one-electron oxidation of these complexes gives the radical-bridged species [(TPyA) 2 Cr 2 ( R L 3−• )] 3+ . Variable-temperature dc susceptibility measurements in these complexes reveal the presence of strong antiferromagnetic metal− semiquinoid radical coupling, with exchange constants of J = −352(10) ( O L 3−• ), − 401(8) ( OS L 3−• ), and −487(8) ( S L 3−• ) cm −1 . These results provide the first measurement of magnetic coupling between metal ions and a thiosemiquinoid radical, and they demonstrate the value of moving from O to S donors in radical-bridged metal ions in the design of magnetic molecules and materials.

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Section: ■ Introductionmentioning

confidence: 87%

Thiosemiquinoid Radical-Bridged Cr^III₂ Complexes with Strong Magnetic Exchange Coupling

2019

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“…Multinuclear metal complexes are an intriguing class of materials due to not only their fascinating structures [1][2][3][4][5][6][7][8][9] but also their unique redox [10][11][12][13][14][15] , magnetic [16][17][18] and photochemical properties 19,20 and reactivity [21][22][23][24][25][26] . Due to these attractive properties, multinuclear metal complexes play a significant role in several biological systems [27][28][29][30] and are expected to be functional materials for future practical applications [31][32][33][34] (Scheme 1a).…”

Section: Introductionmentioning

confidence: 99%

Precise manipulation of electron transfers in clustered five redox sites

Izu

Kondo

Tomoda

et al. 2021

Preprint

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Electron transfers in multinuclear metal complexes are the origin of their unique functionalities both in natural and artificial systems. However, electron transfers in multinuclear metal complexes are generally complicated, and predicting and controlling these electron transfers is extremely difficult. Herein, we report the precise manipulation of the electron transfers in multinuclear metal complexes. The development of a rational synthetic strategy afforded a series of pentanuclear metal complexes composed of metal ions and 3,5-bis(2-pyridyl)pyrazole (Hbpp) as a platform to probe the phenomena. Electrochemical and spectroscopic investigations clarified the overall picture of the electron transfers in the pentanuclear complexes. In addition, unique electron transfer behaviours, in which the reduction of a metal centre occurs during the oxidation of the overall complex (reduction-upon-oxidation process), were discovered. We also elucidated the two dominant factors that determine the manner of the electron transfers. Our results provide comprehensive guidelines for interpreting the complicated electron transfers in multinuclear metal complexes.

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“…[45,47] Por ejemplo, se han descrito clústeres de fórmula [Mo3CoS4Cl3X(dmpe)3] n+ (X = Cl, n = 1; X = Cl, n = 0; X = CO, n = 0) que presentan configuraciones electrónicas variables, en concreto de 14, 15 y 16 electrones, respectivamente. [48] El diagrama de orbitales propuesto por Harris predice la existencia de tres orbitales moleculares enlazantes asociados a la formación del enlace metal-metal (1e, 1a1 y 2e), dos orbitales no enlazantes (2a1 y 3e) y dos antienlazantes (4e y 3a1).…”

Section: Dimetilfosfolano)etano ((Rr)-me-bpe) (-)-12-bis((2s5s)-2unclassified

“…[20] En este caso, varias especies clúster coexisten durante el proceso catalítico según la monitorización por PSI (Pressurized Sample Infusion) en combinación con espectrometría de masas, lo que imposibilita la identificación de la especie activa. [46,47] hemos elegido la cetona fluorada 2,2,2-trifluoroacetofenona como sustrato modelo, cuya reducción conduce previsiblemente a la formación de α-(trifluorometil)bencil alcohol.…”

Section: Reducción Catalítica De Cetonasunclassified

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Desarrollo de sulfuros clúster de metales del grupo seis y sus aplicaciones catalíticas

Padilla¹

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A Cyclic Hexanuclear Heterometalladithiolene Cluster [{(Cp*Rh)₂Mo(μ‐CO)₂(CO)}₂(S₂C₆H₂S₂)₂] with Two π‐Conjugated S₂C₆S₂ Bridges: Synthesis, Crystal Structure, and Properties

Cited by 5 publications

References 23 publications

Thiosemiquinoid Radical-Bridged Cr^III₂ Complexes with Strong Magnetic Exchange Coupling

Thiosemiquinoid Radical-Bridged Cr^III₂ Complexes with Strong Magnetic Exchange Coupling

Precise manipulation of electron transfers in clustered five redox sites

Desarrollo de sulfuros clúster de metales del grupo seis y sus aplicaciones catalíticas

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A Cyclic Hexanuclear Heterometalladithiolene Cluster [{(Cp*Rh)2Mo(μ‐CO)2(CO)}2(S2C6H2S2)2] with Two π‐Conjugated S2C6S2 Bridges: Synthesis, Crystal Structure, and Properties

Cited by 5 publications

References 23 publications

Thiosemiquinoid Radical-Bridged CrIII2 Complexes with Strong Magnetic Exchange Coupling

Thiosemiquinoid Radical-Bridged CrIII2 Complexes with Strong Magnetic Exchange Coupling

Precise manipulation of electron transfers in clustered five redox sites

Desarrollo de sulfuros clúster de metales del grupo seis y sus aplicaciones catalíticas

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Product

Resources

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A Cyclic Hexanuclear Heterometalladithiolene Cluster [{(Cp*Rh)₂Mo(μ‐CO)₂(CO)}₂(S₂C₆H₂S₂)₂] with Two π‐Conjugated S₂C₆S₂ Bridges: Synthesis, Crystal Structure, and Properties

Thiosemiquinoid Radical-Bridged Cr^III₂ Complexes with Strong Magnetic Exchange Coupling

Thiosemiquinoid Radical-Bridged Cr^III₂ Complexes with Strong Magnetic Exchange Coupling