The<i>trans</i>influence of the pyridine ligand on ruthenium(II)–porphyrin–carbene complexes

Harada, Tomoko; Wada, Satoko; Yuge, Hidetaka; Miyamoto, Takeshi

doi:10.1107/s0108270102022461

Cited by 14 publications

(3 citation statements)

References 6 publications

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“…A similar situation has been previously observed with other porphyrin ruthenium complexes . The Ru−N distances of 2.042(3)−2.054(3) Å all fall within the range previously reported for diamagnetic ruthenium porphyrin complexes. ,,– The geometry of the coordination sphere is close to an octahedral geometry. Bond angles at ruthenium are in the range 90.02(14)−96.39(14)° for cis angles and 173.08(12)−173.58 (12)° for trans angles.…”

Section: Resultssupporting

confidence: 87%

“…The Ru−C distance of 1.839(4) Å is slightly longer than the ruthenium−carbon double bond (1.829(9) Å) for (TPP)Ru[C(CO 2 Et][MeOH] reported by us some years ago and similar to those reported by Che and Miyamoto. ,– The Ru−O (THF) distance 2.376(3) Å is shorter than the axial Os−O bond (THF, 2.43(2) Å) in a similar carbene osmium complex, reported by Woo et al, as expected from the different size of the two metal atoms.…”

Section: Resultssupporting

confidence: 79%

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Isolation, X-ray Crystal Structure, and Reactivity of a New C−H Carbene Complex of (5,10,15,20-Tetraphenylporphyrinato)ruthenium(II)

et al. 2008

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The new (porphyrin)ruthenium(II) carbene complex 1 has been prepared by treating (TPP)Ru(CO)(EtOH) with excess 2,6-di-tert-butyl-4-methylphenyl diazoacetate and characterized by X-ray crystal structure analysis due to a kinetic stability. The reactivity of 1 toward axial ligands (CO, pyridine, dimethylphenylphosphine) and the asymmetric cyclopropanation of styrene with this bulky diazoacetate ester catalyzed by ruthenium Halterman porphyrin are also presented.

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Section: Resultssupporting

confidence: 87%

Section: Resultssupporting

confidence: 79%

Isolation, X-ray Crystal Structure, and Reactivity of a New C−H Carbene Complex of (5,10,15,20-Tetraphenylporphyrinato)ruthenium(II)

et al. 2008

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“…The observation of trans influence and trans effect in ruthenium complexes has been reported previously, specifically with phosphine and py-type ligands in the ground state. 98–101 To our knowledge, there are no reports of trans influence in the excited state that directly results in ligand dissociation. From the results of the Mulliken spin density calculations, in combination with the CDA and MBO analyses, it may be inferred that the high quantum yield of ligand dissociation observed for 2 is associated with the high spin density localized on the quinoline moiety in the mixed 3 MLCT/ 3 ππ * excited state.…”

Section: Calculationsmentioning

confidence: 99%

Unusual Role of Excited State Mixing in the Enhancement of Photoinduced Ligand Exchange in Ru(II) Complexes

Loftus

Fillman

et al. 2017

J. Am. Chem. Soc.

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Four Ru(II) complexes were prepared bearing two new tetradentate ligands, cyTPA and 1-isocyTPQA, which feature a piperidine ring that provides a structurally rigid backbone and facilitates the installation of other donors as the fourth chelating arm, while avoiding the formation of stereoisomers. The photophysical properties and photochemistry of [Ru(cyTPA)(CH3CN)2]2+ (1), [Ru(1-isocyTPQA)(CH3CN)2]2+ (2), [Ru(cyTPA)(py)2]2+ (3), and [Ru(1-isocyTPQA)-(py)2]2+ (4) were compared. The quantum yield for the CH3CN/H2O ligand exchange of 2 was measured to be Φ400 = 0.033(3), 5-fold greater than that of 1, Φ400 = 0.0066(3). The quantum yields for the py/H2O ligand exchange of 3 and 4 were lower, 0.0012(1) and 0.0013(1), respectively. DFT and related calculations show the presence of a highly mixed 3MLCT/3ππ* excited state as the lowest triplet state in 2, whereas the lowest energy triplet states in 1, 3, and 4 were calculated to be 3LF in nature. The mixed 3MLCT/3ππ* excited state places significant spin density on the quinoline moiety of the 1-isocyTPQA ligand positioned trans to the photolabile CH3CN ligand in 2, suggesting the presence of a trans-type influence in the excited state that enhances ligand exchange. Ultrafast spectroscopy was used to probe the excited states of 1–4, which confirmed that the mixed 3MLCT/3ππ* excited state in 2 promotes ligand dissociation, representing a new manner to effect photoinduced ligand exchange. The findings from this work can be used to design improved complexes for applications that require efficient ligand dissociation, as well as for those that require minimal deactivation of the 3MLCT state through low-lying metal-centered states.

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Palladium Nanoparticles on Thermoresponsive Hydrogels and their Application as Recyclable Suzuki–Miyaura Coupling Reaction Catalysts in Water

et al. 2012

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Thetransinfluence of the pyridine ligand on ruthenium(II)–porphyrin–carbene complexes

Cited by 14 publications

References 6 publications

Isolation, X-ray Crystal Structure, and Reactivity of a New C−H Carbene Complex of (5,10,15,20-Tetraphenylporphyrinato)ruthenium(II)

Isolation, X-ray Crystal Structure, and Reactivity of a New C−H Carbene Complex of (5,10,15,20-Tetraphenylporphyrinato)ruthenium(II)

Unusual Role of Excited State Mixing in the Enhancement of Photoinduced Ligand Exchange in Ru(II) Complexes

Palladium Nanoparticles on Thermoresponsive Hydrogels and their Application as Recyclable Suzuki–Miyaura Coupling Reaction Catalysts in Water

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