Synthesis and Characterization of Dithia[3.3]metaparacyclophane‐Bridged Dimetallic Ruthenium Acetylide Complexes

Xia, Jianlong; Ou, Ya‐Ping; Meng, Xiang‐Gao; Yin, Jun; Yu, Guang‐Ao; Liu, Sheng Hua

doi:10.1002/ejic.201301304

Cited by 12 publications

(5 citation statements)

References 60 publications

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“…These intermediates acted as the starting materials for the syntheses of precursors 1b and 2b . Finally, the TMS‐protected compounds 1b and 2b were deprotected using KF and reacted in situ with (RuCl[dppe]Cp*) under reflux conditions . The target complexes 1–2 were obtained through filtration and characterized using conventional spectroscopic methods.…”

Section: Resultssupporting

confidence: 82%

See 1 more Smart Citation

Phenyl‐Bridged Ferrocene/Ruthenium Alkynyl Heterobimetallic Complexes: Syntheses, Characterization, and Electrochemical, Spectroscopic, and Computational Investigation

Wang

Yuan

et al. 2020

Eur J Inorg Chem

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Two isomeric phenyl‐bridged ferrocenyl and ruthenium alkynyl complexes 1 and 2 are synthesized and characterized through NMR, elemental analysis, and X‐ray single‐crystal diffraction. The electronic properties of the complexes are investigated via electrochemical studies, UV/Vis‐NIR and IR spectroelectrochemistry, and theoretical calculations. Cyclic voltammetry and square‐wave voltammetry technologies show two successive redox behaviors from Ru(II) and ferrocenyl centers in 1 and 2, respectively. These behaviors are supported by the dominant spin–spin density distribution in RuCp*(dppe) terminals. The large potential difference (ΔE1/2) and comproportionation constants (Kc) observed in complex 1 suggest that 1+ has better chemical stability than 2+. Strong electronic communication from 1+ are detected through the observed NIR absorption band in 1+ and large Δν(C≡C) value of 1→1+. The broad NIR absorption in 1+ is reproduced and assigned to ferrocenyl to the Ru(III) center charge transfer transition with major contributions from the β‐HOSO→β‐LUSO transition.

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Section: Resultssupporting

confidence: 82%

“…The reagents 4‐bromoaniline, 3‐bromoaniline, ferrocene, trimethylsilylacetylene, KF, Pd(PPh 3 ) 4 and NaNO 2 were commercially available. RuCp*(dppe)Cl and Intermediates 1a , 2a , 1b and 2b were prepared by similar reported literature , …”

Section: Methodsmentioning

confidence: 99%

Phenyl‐Bridged Ferrocene/Ruthenium Alkynyl Heterobimetallic Complexes: Syntheses, Characterization, and Electrochemical, Spectroscopic, and Computational Investigation

Wang

Yuan

et al. 2020

Eur J Inorg Chem

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“…Alkenyl ruthenium complexes of the type (ArCHCH){Ru(CO)Cl(P i Pr 3 ) 2 } (Ar = aryl) have similar properties to TAs. − They also feature a reversible one-electron oxidation whose half-wave potential falls close to that of common TAs and depends on the substitution pattern of the attached aryl unit, as well as delocalized frontier orbitals with large contributions of the alkenyl ligand. ,− As an added benefit, the oxidation-induced shift of the CO stretching vibration of the metal-bonded carbonyl ligand as well as usually resolved hyperfine splittings of the unpaired electron spin to the 31 P nuclei of the phosphine ligands render the {Ru(CO)Cl(P i Pr 3 ) 2 } complex entity (henceforth denoted as {Ru}) a sensitive indicator of the charge and spin density distributions over the alkenyl ligand and the metal ion. − ,− The attachment of a TA tag to the alkenyl ligands of such ruthenium complexes has provided examples of electronically strongly coupled or even intrinsically delocalized asymmetric MV systems as is exemplified by the one-electron oxidized form of the complex {Ru}{−CHCH–C 6 H 4 N(C 6 H 4 -4-OMe) 2 } ( Ru-TAOMe ). , Introducing electron-donating or electron-withdrawing substituents to the TA entity has allowed us to study how a less symmetric charge and spin density distribution impacts on the shape and the intensity of the ensuing IVCT band. − Closely related alkynyl ruthenium–TA conjugates with Cp*(dppe)Ru–CC– instead of the {Ru}–CHCH– tag have also been scrutinized with respect to the MV properties of their associated radical cations and were found to have a more Ru-alkynyl centered oxidation with a concomitant bias of the unipositive charge and the unpaired spin density to the metal site and a concomitantly weaker electronic coupling. , …”

Section: Introductionmentioning

confidence: 99%

Charge and Spin Delocalization in Mixed-Valent Vinylruthenium–Triarylamine-Conjugates with Planarized Triarylamines

et al. 2022

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We report on three new vinylruthenium−triarylamine (TA) conjugates with planarized TA substituents. The neutral, mono-, and dioxidized forms of the complexes were scrutinized by UV/vis/NIR, IR, and EPR spectroscopies as well as by quantum chemical calculations. By analyzing the intervalence charge-transfer (IVCT) transitions of the mixed-valent radical cations, we obtain information on the extent of electronic coupling between the chemically different redox sites. Completely delocalized Ru-MeTA + shows a vibrationally structured, nonsolvatochromic IVCT band. Decreased blueshifts of the indicative Ru(CO) stretching vibration during the first oxidation and larger A( 14 N) EPR hyperfine splitting constants in concert with smaller gvalues indicate enhanced TA contributions to the singly occupied molecular orbital of the other two complexes Ru-TOTA •+ and Ru-DOTA •+ and hence less symmetrical charge and spin density distributions. This is also reflected by the solvatochromism and the asymmetric shape of the IVCT band with a smaller bandwidth at the low-energy side. Temperature-dependent UV/vis/NIR spectroscopy of mixed-valent Ru-TOTA •+ and Ru-DOTA •+ revealed that the band skewing is due to the vibrational coupling of the IVCT transition to symmetrical vibrations, placing these radical cations near or at the class II/III borderline according to Robin and Day.

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“…125 cm –1 for similar carbonylphosphine complexes with a mainly metal-centered HOMO . Both have shown to be extremely useful in elucidating the degree of charge and spin delocalization in arylene-bridged, MV bis(vinylruthenium) complexes. − ,,− …”

Section: Introductionmentioning

confidence: 99%

Manipulation and Assessment of Charge and Spin Delocalization in Mixed-Valent Triarylamine–Vinylruthenium Conjugates

Hassenrück

Winter

2017

Inorg. Chem.

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Triarylamine-vinylruthenium conjugates (4-RCH)N{CH-4-CH═CHRu(CO)Cl(PPr)}, with R = CHO (1-CHO), C(═O)Me (1-Ac), COOMe (1-E), and Me (1-Me), have been prepared and investigated in their neutral, mono- and dioxidized states by cyclic voltammetry, IR, and UV/vis/near-infrared spectroelectrochemistry, electron paramagnetic resonance spectroscopy, and quantum-chemical calculations. Electron-withdrawing substituents at the triarylamine moiety shift the charge and spin density toward the more electron-rich vinylruthenium site in comparison to the 4-OMe-substituted triarylamine-vinylruthenium conjugate 1-OMe. A more asymmetric charge distribution changes the intense vibrationally structured intervalence charge-transfer (IVCT) band of completely delocalized, mixed-valent (MV) 1-OMe to a weaker, highly asymmetric, nonsolvatochromic band with significantly smaller bandwidth at the low-energy side. The temperature dependence of the IVCT band of the formyl derivative 1-CHO proves that vibrational coupling of the IVCT transition to a symmetrical vibration is the underlying reason for band skewing. All of our results indicate that the MV radical cations remain electronically strongly coupled despite an increasingly stronger bias of the highest occupied molecular orbital to the vinylruthenium entity. Moreover, the dications of these complexes were found to be paramagnetic, which makes them rare examples of compounds that combine strong electronic coupling in the cationic MV state with paramagnetism of the dications.

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Synthesis and Characterization of Dithia[3.3]metaparacyclophane‐Bridged Dimetallic Ruthenium Acetylide Complexes

Cited by 12 publications

References 60 publications

Phenyl‐Bridged Ferrocene/Ruthenium Alkynyl Heterobimetallic Complexes: Syntheses, Characterization, and Electrochemical, Spectroscopic, and Computational Investigation

Phenyl‐Bridged Ferrocene/Ruthenium Alkynyl Heterobimetallic Complexes: Syntheses, Characterization, and Electrochemical, Spectroscopic, and Computational Investigation

Charge and Spin Delocalization in Mixed-Valent Vinylruthenium–Triarylamine-Conjugates with Planarized Triarylamines

Manipulation and Assessment of Charge and Spin Delocalization in Mixed-Valent Triarylamine–Vinylruthenium Conjugates

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