Synthesis and crystal structure of high and low spin diruthenium complexes with diphenylformamidine and diphenyltriazene ligands

Barral, M.C.; González‐Prieto, Rodrigo; Herrero, Santiago Montero; Jiménez‐Aparicio, Reyes; Priego, José L.; Royer, E.C.; Torres, M. Rosario; Urbanos, Francisco A.

doi:10.1016/j.poly.2004.05.015

Cited by 41 publications

(54 citation statements)

References 27 publications

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“…[24] The magnetic moment of this complex [25] at room temperature is in accord with a S = 3 = 2 system with the usual (p* d*) 3 HOMO. However, the substitution of the axial chloride by a NCS À ligand leads to the [25] which indicates a p* 3 or d* 2 p* electronic configuration.…”

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: 71%

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

Barral

Casanova

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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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: 71%

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

Barral

Casanova

Herrero

et al. 2010

Chemistry A European J

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“…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. The m eff value at room temperature corresponds to the presence of two unpaired electrons (3.09 m B ).…”

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confidence: 88%

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confidence: 99%

“…[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. [9] The high sensitivity of the magnetic moment to the nature of the axial ligand in this class of compounds challenged us to find the limit at which the difference in energy between the p* and d* levels becomes similar to the electron-pairing energy.…”

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confidence: 99%

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A Spin‐Admixed Ruthenium Complex

et al. 2004

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“…Finally, we point out that some papers have suggested that the low spin state of Ru-based complexes can be π * 3 rather than δ * 2 π * . This narrative implies that the π * orbital lies lower than the δ * orbital 51,59 . With spin on the diruthenium complex decreasing from S = 3/2 to S = 1/2 at 0.8 GPa, the sublattice spin changes sign and points along the Cr spin direction.…”

Section: Rumentioning

confidence: 98%

Pressure-driven high-to-low spin transition in the bimetallic quantum magnet[Ru2(O2CMe)4]3
O’Neal
¹
,
Liu
²
,
Miller
³

et al. 2014
Phys. Rev. B
15
0
3
0
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Synchrotron-based infrared and Raman spectroscopies were brought together with diamond anvil cell techniques and an analysis of the magnetic properties to investigate the pressure-induced high → low spin transition in [Ru2(O2CMe)4]3[Cr(CN)6]. The extended nature of the diruthenium wavefunction combined with coupling to chromium-related local lattice distortions changes the relative energies of the π * and δ * orbitals and drives the high → low spin transition on the mixed-valence diruthenium complex. This is a rare example of an externally controlled metamagnetic transition in which both spin-orbit and spin-lattice interactions contribute to the mechanism.

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Synthesis and crystal structure of high and low spin diruthenium complexes with diphenylformamidine and diphenyltriazene ligands

Cited by 41 publications

References 27 publications

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

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

A Spin‐Admixed Ruthenium Complex

Pressure-driven high-to-low spin transition in the bimetallic quantum magnet[Ru2(O2CMe)4]3
O’Neal
¹
,
Liu
²
,
Miller
³

et al. 2014
Phys. Rev. B
15
0
3
0
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Synthesis and crystal structure of high and low spin diruthenium complexes with diphenylformamidine and diphenyltriazene ligands

Cited by 41 publications

References 27 publications

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

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

A Spin‐Admixed Ruthenium Complex

Pressure-driven high-to-low spin transition in the bimetallic quantum magnet[Ru2(O2CMe)4]3O’Neal1, Liu2, Miller3 et al. 2014Phys. Rev. B15030View full textAdd to dashboardCite

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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

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

Pressure-driven high-to-low spin transition in the bimetallic quantum magnet[Ru2(O2CMe)4]3
O’Neal
¹
,
Liu
²
,
Miller
³

et al. 2014
Phys. Rev. B
15
0
3
0
View full text Add to dashboard Cite