A Spin‐Admixed Ruthenium Complex

Barral, M.C.; Herrero, Santiago Montero; Jiménez‐Aparicio, Reyes; Torres, M. Rosario; Urbanos, Francisco A.

doi:10.1002/ange.200461463

Cited by 24 publications

(41 citation statements)

References 26 publications

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“…1 was prepared by adding AgBF 4 (0.118 g, 0.606 mmol) to a suspension of [Ru 2 Cl(m-O 2 CMe)(m-DPhF) 3 ] [8] (0.526 g, 0.596 mmol) in 10 mL of THF. The mixture was protected from light and stirred for 1 day.…”

Section: Methodsmentioning

confidence: 99%

“…The water molecule is coordinated to the axial positions of the diruthenium units with 50 % occupancy. The metal-metal bond (2.3503 (9) ) is longer than in the parent compounds [Ru 2 Cl(m-O 2 CMe)(m-DPhF) 3 ] (2.3203(5) ) [8] and [Ru 2 (NCS)(m-O 2 CMe)(m-DPhF) 3 ] (2.3182 (11) ). [7] Complex 1 shows exceptional magnetic behavior (Figure 2), intermediate between those observed for the chloro and the isothiocyanato derivatives.…”

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confidence: 97%

“…[6,7] Moreover, [Ru 2 Cl(m-O 2 CMe)(m-DPhF) 3 ] (DPhF = N,N'-diphenylformamidinate) [8] has three unpaired electrons, whereas the derivative [Ru 2 (NCS)(m-O 2 CMe)(m-DPhF) 3 ] is a low-spin complex with only one unpaired electron. [7] Chen and Ren also reported high-and low-spin diruthenium(iii) complexes with the same core but different axial ligands.…”

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A Spin‐Admixed Ruthenium Complex

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A Spin‐Admixed Ruthenium Complex

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“…[32][33][34][35][36][37] However, the examples with the second-and thirdrow transition metals are known only for the above-mentioned diruthenium complexes. [25,[29][30][31]38] In some of these compounds the S = 1 = 2 and S = 3 = 2 spin states are sufficiently close in energy that either can be obtained by variation of the axial ligand. Therefore, it would be useful to know if the control of the spin state of these complexes is possible.…”

Section: -A C H T U N G T R E N N U N G (O 2 Cme)a C H T U N G T R E mentioning

confidence: 96%

Tuning the Magnetic Moment of [Ru₂(DPhF)₃(O₂CMe)L]⁺ Complexes (DPhF=N,N′‐Diphenylformamidinate): A Theoretical Explanation of the Axial Ligand Influence

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Herrero

et al. 2010

Chemistry A European J

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The magnetic behaviour of the compounds containing the [Ru(2)(DPhF)(3)(O(2)CMe)](+) ion (DPhF(-)=N,N'-diphenylformamidinate) shows a strong dependence on the nature of the ligand bonded to the axial position. The new complexes [Ru(2)(DPhF)(3)(O(2)CMe)(OPMe(3))][BF(4)]0.5 CH(2)Cl(2) (1 0.5 CH(2)Cl(2)) and [Ru(2)(DPhF)(3)(O(2)CMe)(4-pic)][BF(4)] (2) (4-pic=4-methylpyridine) clearly display this influence. Complex 1.0.5 CH(2)Cl(2) shows a magnetic moment corresponding to a S=3/2 system affected by the common zero-field splitting (ZFS) and a weak antiferromagnetic interaction, whereas complex 2 displays an intermediate behaviour between S=3/2 and S=1/2 systems. The experimental data of complex 1 are fitted with a model that considers the ZFS effect using the Hamiltonian H(D)=S.D.S. The weak antiferromagnetic coupling is introduced as a perturbation, using the molecular field approximation. DFT calculations demonstrate that, in the [Ru(2)(O(2)CMe)(DPhF)(3)(L)](+) complexes, the energy level of the metal-metal molecular orbitals is strongly dependent on the nature of the axial ligand (L). This study reveals that the increase in the pi-acceptor character of L leads to a greater split between the pi* and delta* HOMO orbitals. The influence of the axial ligand in the relative energy between the doublet and quartet states in this type of complexes was also analysed. This study was performed on the new complexes 1.0.5 CH(2)Cl(2) and 2. The previously isolated [Ru(2)(DPhF)(3)(O(2)CMe)(OH(2))][BF(4)].0.5 CH(2)Cl(2) (3.0.5 CH(2)Cl(2)) and [Ru(2)(DPhF)(3)(O(2)CMe)(CO)][BF(4)].CH(2)Cl(2) (4.CH(2)Cl(2)) complexes were also included in this study as representative examples of spin-admixed and low-spin configurations, respectively. The [Ru(2)(DPhF)(3)(O(2)CMe)](+) (5) unit was used as a reference compound. These theoretical studies are in accordance with the different magnetic behaviour experimentally observed.

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“…3+ (adc-R = azodicarbonyl ligands, see Scheme 4), on the other hand, are EPR silent even at 4 K, [67,96] in spite of an S = (M = Ru or Os, [54b, 96] ) or of other multinuclear ruthenium compounds [97] show spin-orbit-coupling-enhanced spin admixture of S = 1 = 2 and S = 3 = 2 states which requires further investigation.…”

Section: The Heavy-metal Effect: Ruthenium Versus Osmiummentioning

confidence: 99%

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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A Spin‐Admixed Ruthenium Complex

Cited by 24 publications

References 26 publications

A Spin‐Admixed Ruthenium Complex

A Spin‐Admixed Ruthenium Complex

Tuning the Magnetic Moment of [Ru₂(DPhF)₃(O₂CMe)L]⁺ Complexes (DPhF=N,N′‐Diphenylformamidinate): A Theoretical Explanation of the Axial Ligand Influence

Unconventional Mixed‐Valent Complexes of Ruthenium and Osmium

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A Spin‐Admixed Ruthenium Complex

Cited by 24 publications

References 26 publications

A Spin‐Admixed Ruthenium Complex

A Spin‐Admixed Ruthenium Complex

Tuning the Magnetic Moment of [Ru2(DPhF)3(O2CMe)L]+ Complexes (DPhF=N,N′‐Diphenylformamidinate): A Theoretical Explanation of the Axial Ligand Influence

Unconventional Mixed‐Valent Complexes of Ruthenium and Osmium

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Tuning the Magnetic Moment of [Ru₂(DPhF)₃(O₂CMe)L]⁺ Complexes (DPhF=N,N′‐Diphenylformamidinate): A Theoretical Explanation of the Axial Ligand Influence