Ruthenium(iii)-promoted oxidative dimerization of aniline to N-phenyl-1,2-phenylenediimine. Definitive proof for the template reaction

Mitra, Kedar Nath; Majumdar, Partha; Peng, Shie‐Ming; Castiñeiras, Alfonso; Goswami, Sreebrata

doi:10.1039/a702047c

Cited by 48 publications

(20 citation statements)

References 5 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Dimethylglyoxime ligand is coordinated to ruthenium as a bidentate N,N-donor ligand forming five-membered chelate ring with a bite angle of 73.39(2)°. In 1f the Ru-P bond distance is 2.3407(13) Å, and Ru(1)-N(1) and Ru(1)-N(2) bond distances are 2.046(4) and 2.034(4) Å, respectively, shorter than Ru(II)-N lengths where N-donor ligand is not involved in p-interaction with the metal center [53][54][55][56]. The C-N lengths within the coordinated dioxime ligands are also significantly longer than localized C@N bond [57].…”

Section: X-ray Crystallographymentioning

confidence: 97%

Structures, preparation and catalytic activity of ruthenium cyclopentadienyl complexes based on pyridyl-phosphine ligand

Kumar¹,

Singh²,

Sharma³

et al. 2009

Journal of Organometallic Chemistry

View full text Add to dashboard Cite

Section: X-ray Crystallographymentioning

confidence: 97%

Structures, preparation and catalytic activity of ruthenium cyclopentadienyl complexes based on pyridyl-phosphine ligand

Kumar¹,

Singh²,

Sharma³

et al. 2009

Journal of Organometallic Chemistry

View full text Add to dashboard Cite

“…The C(13)–O(130) bond length, 1.209(4) Å, indicates a localized double bond. The two C–N (imine) bond lengths, 1.300(4) Å [C(12)–N(11)] and 1.290(6) Å [C(25)–N(26)], respectively confirm6a,13 their double bond character. The six Ru–N lengths are similar, and lie in the range 1.997–2.083 Å.…”

Section: Resultsmentioning

confidence: 78%

Two Novel Reactions of a Ruthenium‐Coordinated Phenazine – Oxidative Aromatic Ring Hydroxylation and Dimerization via a New C–N Bond Formation

et al. 2007

Self Cite

View full text Add to dashboard Cite

The reaction of [Ru(CH3OH)2(N∧N)2]2+ [N∧N = 2,2′‐bipyridine (bpy) and 1,10‐ortho‐phenanthroline(phen)] with the phenazine ligand, [HL1 = 6‐p‐anisyl‐2‐(p‐anisylamino)‐3(4H)‐p‐anisylimine‐9‐methoxyphenazine] in the presence of a base (NEt3) afforded two mononuclear ruthenium complexes, [Ru(L1)(N∧N)2]X (2), and [Ru(LO)(N∧N)2]X2 (3), [LO = 7‐methoxy‐5‐(4‐methoxyphenyl)‐2,3‐bis(4‐methoxyphenylimino)‐3,5‐dihydro‐2H‐phenazin‐1‐one] together with a diruthenium complex [(N∧N)2RuL2Ru(N∧N)2]X3 (4), [L2 = 7,8′‐dimethoxy‐5,10′‐bis(4‐methoxyphenyl)‐2,3′‐bis(4‐methoxyphenylamino)‐3,2′‐bis(4′‐methoxyphenylimino)‐3,5,2′,10′‐tetrahydro‐[1,5′]biphenazinyl‐5′‐ylium], (X = ClO4– or CF3SO3–). The complexes 3 and 4 were also obtained from the pure complex 2 under two different experimental conditions. Oxidative aromatic ring hydroxylation of the complex 2 produced 3 while the diruthenium complex, 4, was formed by dimerization of 2 via a new C–N bond formation. The products were thoroughly characterized with the help of 1H NMR and ESI‐MS spectral measurements. Final authentication of the two complexes of the transformed phenazine ligands viz. 3 and 4 were made by single‐crystal X‐ray structure determination of the two representative complexes. These compounds are intensely colored and show transitions in the visible region, which are ascribed as metal‐to‐ligand charge transfer (MLCT). Notably, intensities of the two MLCT of the compound 4 are significantly higher than those of 2 and 3. Redox properties of the complexes are reported. Electrochemical oxidation of compound 2, even in the presence of trace moisture, produced compound 3. Cyclic voltammetry of compound 3 shows a reductive response near–0.35 V. Its one‐electron reduced product is blue and shows an intense EPR signal at g = 2.001. The voltammogram of the diruthenium complex 4 consists of two responses near 0.70 and 0.85 V. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007)

show abstract

“…[9,22] The NÀ H stretching vibrations of complexes 3 and 4 occur at around 3415 cm À 1 , which are comparable to arylamine species. [23] The proton (acacÀ H) resonances exhibit as a typical singlet peak in the region of 5.3-5.5 ppm in the bis(acetylacetonato) ruthenium(II) complexes 2, 3 and 4. Both complexes 3 and 4 show the NÀ H proton resonances at around 10.10 and 10.50 ppm, and complex 3 displays the methyl protons (acacÀ CH 3 ) ranging from ca 1.79-2.43 ppm to ca 2.30-2.38 ppm compared with 4, which agreed well with the typical values (1.7-2.4 ppm) in the literatures.…”

Section: Results Discussionmentioning

confidence: 99%

Photocatalytic Properties and Electronic Effects of Incorporation Bis(acetylacetonato) Ruthenium(II/III) Complexes with Bidentate Nitrogen and Sulfur Ancillaries

et al. 2021

View full text Add to dashboard Cite

Treatment of cis-[Ru(acac) 2 (CH 3 CN) 2 ] (acac À = acetylacetonate) with 1.5 equiv. of corresponding bidentate nitrogen and sulfur ligands in ethanol gave a series of bis(acetylacetonato) ruthenium(II/III) complexes [(acac 4) and [(acac) 2 Ru(S 2 CNMe 2 )] (5), respectively.Complexes 1-5 were characterized by FT-IR, NMR and UV-Vis spectroscopies along with their electrochemical properties. The structures of complexes 1-5 have been unambiguously established by single crystal X-ray crystallography. The photocatalytic properties for hydrogen production by water splitting of complexes 1-5 under visible light (λ > 420 nm) were also investigated in the paper.

show abstract

Ruthenium(iii)-promoted oxidative dimerization of aniline to N-phenyl-1,2-phenylenediimine. Definitive proof for the template reaction

Abstract: Fig. 2 Molecular structure of [RuCl 2 (PhNH 2 ) 2 L] 3 showing the atom numbering scheme. Selected bond distances (Å):

Cited by 48 publications

References 5 publications

Structures, preparation and catalytic activity of ruthenium cyclopentadienyl complexes based on pyridyl-phosphine ligand

Structures, preparation and catalytic activity of ruthenium cyclopentadienyl complexes based on pyridyl-phosphine ligand

Two Novel Reactions of a Ruthenium‐Coordinated Phenazine – Oxidative Aromatic Ring Hydroxylation and Dimerization via a New C–N Bond Formation

Photocatalytic Properties and Electronic Effects of Incorporation Bis(acetylacetonato) Ruthenium(II/III) Complexes with Bidentate Nitrogen and Sulfur Ancillaries

Contact Info

Product

Resources

About