Synthesis, characterization and reactivity of polypyridyl ruthenium(II) carbonyl complexes with phosphine derivatives: Ruthenium–carbon bond labilization based on steric and electronic effects

Ooyama, Dai; Saito, Madoka

doi:10.1016/j.ica.2005.04.040

Cited by 6 publications

(12 citation statements)

References 24 publications

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“…The Ru-P bond distances of bis-phosphine complexes (2.4306(7) Å for 2, 2.430(2) and 2.436(2) Å for 3) are longer than that of the 2.3272(7) Å distance in 8, which has a trans chlorido ligand. However, these distances are in the range previously observed in Ru(II)-phosphine complexes [15][16][17][18]. The nitrile units (N≡CR) are essentially linear and the Ru-N, N-C, and C-C bond distances are similar to typical values in other Ru(II)-N≡CR complexes [15].…”

Section: Molecular Structuressupporting

confidence: 55%

“…However, these distances are in the range previously observed in Ru(II)-phosphine complexes [15][16][17][18]. The nitrile units (N≡CR) are essentially linear and the Ru-N, N-C, and C-C bond distances are similar to typical values in other Ru(II)-N≡CR complexes [15]. The phenyl ring of benzonitrile in 3 is nearly coplanar with dnp; the dihedral angle between the central pyridyl ring and the phenyl ring is 13.0(4)°.…”

Section: Molecular Structuressupporting

confidence: 46%

“…This geometry is attributed to steric hindrance between the phenyl rings of PPh 3 and PhCN. In addition, the bond distance of Ru-Cl (2.4412(7) Å) in 8 is within the typical range for Ru(II)-chlorido complexes bearing tridentate pyridyl ligands [15]. A remarkable structural feature is that the interatomic distances between noncoordinating nitrogen atoms of dnp are short.…”

Section: Molecular Structuresmentioning

confidence: 52%

“…As a result, dnp is a much better charge acceptor. This difference is evidenced by the absorption maxima of 8 and the corresponding terpyridine analogue ([Ru(tpy)(PPh 3 )(CH 3 CN)Cl] + ), where the latter (tpy-complex) MLCT band is at 466 nm [15], and 8 absorbs at 563 nm. It is worth noting that the more planar system gives rise to a better delocalization and consequently exhibits lower energy absorption.…”

Section: Electronic Absorption Spectramentioning

confidence: 99%

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Facile and Selective Synthetic Approach for Ruthenium Complexes Utilizing a Molecular Sieve Effect in the Supporting Ligand

et al. 2013

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It is extremely important for synthetic chemists to control the structure of new compounds. We have constructed ruthenium-based mononuclear complexes with the tridentate 2,6-di(1,8-naphthyridin-2-yl)pyridine (dnp) ligand to investigate a new synthetic approach using a specific coordination space. The synthesis of a family of new ruthenium complexes containing both the dnp and triphenylphosphine (PPh 3 ) ligands,, has been described. All complexes have been spectroscopically characterized in solution, and the nitrile complexes have also been characterized in the solid state through single-crystal X-ray diffraction analysis. Dnp in the present complex system behaves like a "molecular sieve" in ligand replacement reactions. Both experimental data and density functional theory (DFT) calculations suggest that dnp plays a crucial role in the selectivity observed in this study. The results provide useful information toward elucidating this facile and selective synthetic approach to new transition metal complexes. OPEN ACCESSInorganics 2013, 1 33

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Section: Molecular Structuressupporting

confidence: 55%

Section: Molecular Structuressupporting

confidence: 46%

Section: Molecular Structuresmentioning

confidence: 52%

Section: Electronic Absorption Spectramentioning

confidence: 99%

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Facile and Selective Synthetic Approach for Ruthenium Complexes Utilizing a Molecular Sieve Effect in the Supporting Ligand

et al. 2013

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“…Interestingly, this particular orientation of the ancillary ligands (PPh 3 and Cl) relative to CO in 2 has been noted in another ruthenium monocarbonyl complex [Ru(Cl)(CO)-(terpy)(PPh 3 )]PF 6 , which features the planar tridentate 2,2′:6′,2″-terpyridine (terpy) ligand. 30 The Ru−P bond length at 2.4719( 7 32 This lengthening of the Ru−P bond is expected because, unlike these latter carbonyl complexes, the PPh 3 ligand is trans to CO in 2. The short Ru−C(O) bond distance [1.923( 2) Å] and the almost linear Ru−C(O) bond angle are both typical of ruthenium(II) phosphinecarbonyl complexes.…”

Section: ■ Syntheses and Interconversionsmentioning

confidence: 98%

Photoactivity of Mono- and Dicarbonyl Complexes of Ruthenium(II) Bearing an N,N,S-Donor Ligand: Role of Ancillary Ligands on the Capacity of CO Photorelease

et al. 2013

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One monocarbonyl and one dicarbonyl complex of ruthenium(II), namely, [Ru(Cl)(CO)(qmtpm)(PPh3)]BF4 (2) and [Ru(Cl)(CO)2(qmtpm)]ClO4 (3), derived from the tridentate ligand 2-quinoline-N-(2'-methylthiophenyl)methyleneimine (qmtpm) have been synthesized and structurally characterized. The qmtpm ligand binds in a meridional fashion in these carbonyl complexes, and in 3, the two carbon monoxide (CO) ligands are cis to each other. Solutions of 2 in ethanol, chloroform, or acetonitrile rapidly release CO upon illumination with low-power (3-15 mW) light in the 300-450 nm range. Loss of CO from 2 brings about a dramatic color change from yellow to magenta because of the formation of [Ru(Cl)(MeCN)(qmtpm)(PPh3)]BF4 (4). In acetonitrile, photorelease of CO from 3 under 360 nm light occurs in two steps, and the violet photoproduct [Ru(Cl)(MeCN)2(qmtpm)](+) upon reaction with Ag(+) and PPh3 affords red [Ru(MeCN)2(qmtpm)(PPh3)](ClO4)2 (5). The structure of 5 has also been determined by X-ray crystallography. Reduced myoglobin assay confirms that 2 and 3 act as photoactive CO-releasing molecules (photoCORMs) that deliver 1 and 2 equiv of CO, respectively. The results of density functional theory (DFT) and time-dependent DFT studies confirm that electronic transitions from molecular orbitals with predominantly Ru-CO character to ligand-based π* orbitals facilitate CO release from these two photoCORMs. Complexes 2-5 have provided an additional opportunity to analyze the roles of the ancillary ligands, namely, PPh3, Cl(-), and MeCN, in shifting the positions of the metal-to-ligand charge-transfer bands and the associated sensitivity of the two photoCORMs to different wavelengths of light. Collectively, the results provide helpful hints toward the future design of photoCORMs that release CO upon exposure to visible light.

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Imidazole→imidazolidine. Preparation by reduction of with NaBH4 and characterisation of the products (PyaiR=1-alkyl-2-{3′-(pyridylazo)}imidazole)

Mondal

Mathur

Slawin

et al. 2007

Journal of Organometallic Chemistry

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Synthesis, characterization and reactivity of polypyridyl ruthenium(II) carbonyl complexes with phosphine derivatives: Ruthenium–carbon bond labilization based on steric and electronic effects

Cited by 6 publications

References 24 publications

Facile and Selective Synthetic Approach for Ruthenium Complexes Utilizing a Molecular Sieve Effect in the Supporting Ligand

Facile and Selective Synthetic Approach for Ruthenium Complexes Utilizing a Molecular Sieve Effect in the Supporting Ligand

Photoactivity of Mono- and Dicarbonyl Complexes of Ruthenium(II) Bearing an N,N,S-Donor Ligand: Role of Ancillary Ligands on the Capacity of CO Photorelease

Imidazole→imidazolidine. Preparation by reduction of with NaBH4 and characterisation of the products (PyaiR=1-alkyl-2-{3′-(pyridylazo)}imidazole)

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