Trimetallic complexes containing 1,1′-Rc′(CC)2 units [Rc′=ruthenocene-1,1′-diyl, Ru(η-C5H4–)2]

Bruce, Michael I.; Jevric, Martyn; Perkins, Gary J.; Skelton, Brian W.; White, Allan H.

doi:10.1016/j.jorganchem.2006.11.037

Cited by 14 publications

(7 citation statements)

References 24 publications

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“…The reversible electrochemical behavior of resonance-stabilized metal-alkynyl complexes of ethynylruthenocenes ,,− prompted us to explore ruthenocene derivatives of Fc-Ru Cl . To these ends we prepared and studied the four ruthenocene–vinylruthenium conjugates of Scheme .…”

Section: Introductionmentioning

confidence: 99%

Mixed-Valent Ruthenocene–Vinylruthenium Conjugates: Valence Delocalization Despite Chemically Different Redox Sites

2019

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Ruthenocene–vinylruthenium conjugates Rc/Rc*–CHCH–Ru(CO)(L)(P i Pr3)2 (Rc = (η5-C5H5)Ru(η5-C5H4); Rc* = (η5-C5Me5)Ru(η5-C5H4); L = Cl or κO,O′-acetylacetonato) have been prepared and investigated in their neutral, mono-, and dioxidized states by cyclic voltammetry, IR and UV/vis/NIR spectroelectrochemistry, and EPR spectroscopy. Their corresponding radical cations are (almost) completely delocalized mixed-valent systems as indicated by the low half-widths, the absence of solvatochromism, and the low-energy cutoff of their IVCT bands in the near-infrared (NIR) and their IR and EPR spectroscopic signatures. The degree of electronic coupling even exceeds that of their ferrocene analogs despite comparable differences between the intrinsic half-wave potentials of the vinylruthenium and the metallocenyl entities and substantially smaller half-wave potential splittings, ΔE 1/2, in the ruthenocene congeners. All experimental results are backed by quantum chemical calculations.

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Section: Introductionmentioning

confidence: 99%

Mixed-Valent Ruthenocene–Vinylruthenium Conjugates: Valence Delocalization Despite Chemically Different Redox Sites

2019

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“…Relative to those in ethynylferrocene ( E 1/2 = 0.68 V) and Ru(BPI)(PPh 3 ) 2 (CCPh) ( E 1/2 = 0.40 V), the oxidation potentials of ferrocenyl ( E 1/2 = 0.27 V) and ruthenium ( E 1/2 = 0.78 V) centers show significant cathodic and anodic shifts, respectively. Such a shift implies substantial electronic communication between Fe and Ru redox centers, comparable to that found in previously described Fe–Ru heteronuclear complexes with bridging ferrocenylacetylides. − Since the Fe–Ru complex 3a is structurally unsymmetrical, the potential difference or wave separation due to sequential oxidation of ferrocenyl and ruthenium(II) centers should not be totally ascribed to metal–metal electronic interactions. To minimize metal–metal communication, the distance between Fe and Ru centers is extended using HCCC 6 H 4 C 6 H 4 CCCp 2 Fe ( d Fe···Ru = ca.…”

Section: Results and Discussionmentioning

confidence: 99%

“…The UV–vis–near-IR spectrum of 3a + in CH 2 Cl 2 solution displays a broad near-IR band centered at 1941 nm (ε = 4400 M –1 cm –1 ) with moderate intensity, ascribed most likely to a heterometallic Ru II → Fe III intervalence charge transfer (IVCT) transition. Such a low-energy band disappears upon further oxidation of 3a + to 3a 2+ , as is found in other mixed-valence Ru–Fe complexes containing both ferrocenyl and ruthenium centers. − The experimentally estimated (2960 cm –1 ) half-height width of the near-IR band is comparable to that calculated (3488 cm –1 ) by Hush model theory (Δν 1/2 = (2310ν max ) 1/2 ). Moreover, the IVCT bands of 3a + show solvent-dependent behavior, further implying a moderate coupling between Fe III and Ru II centers to behave as a class II mixed-valence system.…”

Section: Results and Discussionmentioning

confidence: 99%

Electrochemical, Spectroscopic, and Theoretical Studies on Diethynyl Ligand Bridged Ruthenium Complexes with 1,3-Bis(2-pyridylimino)isoindolate

et al. 2014

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A series of ruthenium acetylide complexes [Ru(BPI)(PPh3)2(CCR)] (BPI = 1,3-bis(2-pyridylimino)isoindolate; R = −C6H5 (2), −Cp2Fe (3a), −C6H4C6H4CCCp2Fe (3b)) and bis(acetylide)-linked binuclear ruthenium complexes [{Ru(BPI)(PPh3)2}2(CCRCC)] (R = none (4), 1,4-benzenediyl (5), 1,4-naphthalenediyl (6), 9,10-anthracenediyl (7)) were synthesized and characterized by ESI-MS spectrometry, IR, 1H and 31P NMR, and UV–vis–near-IR spectroscopy, and cyclic and differential pulse voltammetry. Oxidation of 3–7 with 1 equiv of ferrocenium perchlorate afforded the corresponding one-electron-oxidized complexes 3 +–7 +. In contrast to the case for 3a + , where spin density is localized at the Fe center due to moderate electronic communication between RuII and FeIII centers along the Ru–CC–Cp2Fe backbone, the spin density is primarily populated on Ru for 3b + without an appreciable electronic interaction between RuIII and FeII across the quite long bridging system RuCCC6H4C6H4CCCp2Fe. For bis(acetylide)-linked binuclear ruthenium complexes 4–7, electrochemical, UV–vis–near-IR spectral and TD-DFT computational studies reveal that electronic delocalization along the bridging RuCCRCCRu backbone is highly dependent on the R spacer. It is demonstrated that with the gradual increase of a π-conjugated system in aromatic R spacer, the electronic delocalization shows progressive enhancement along the Ru–CCRCC–Ru backbone due to an increasing participation of the bridging ligand. 4 + displays highly electronically delocalized behavior, whereas 5 +–7 + are on the borderline of electronic delocalization.

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“…AuCl(PR 3 ) (R ¼ Ph, tol) [10], Fc'-1,1 0 -(C^CSiMe 3 ) 2 1 [1] and Rc'-1,1 0 -(C^CSiMe 3 ) 2 [11] were made by the cited procedures. of an insoluble polymeric material either as described above, or by treating the bis compound with CuI, as already described for the Ag 2 Au 2 cluster [7].…”

Section: Reagentsmentioning

confidence: 99%

Phosphine-gold(I) derivatives of 1,1′-bis(alkynyl)metallocenes: Molecular structures of Fc’(CCX)2 [X = Au(PPh3), SiMe3] and Au4{(CC)2Fc’}2(PPh3)2 [Fc’ = Fe(η-C5H4-)2]

Bruce

Jevric

Skelton

et al. 2010

Journal of Organometallic Chemistry

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Trimetallic complexes containing 1,1′-Rc′(CC)2 units [Rc′=ruthenocene-1,1′-diyl, Ru(η-C5H4–)2]

Cited by 14 publications

References 24 publications

Mixed-Valent Ruthenocene–Vinylruthenium Conjugates: Valence Delocalization Despite Chemically Different Redox Sites

Mixed-Valent Ruthenocene–Vinylruthenium Conjugates: Valence Delocalization Despite Chemically Different Redox Sites

Electrochemical, Spectroscopic, and Theoretical Studies on Diethynyl Ligand Bridged Ruthenium Complexes with 1,3-Bis(2-pyridylimino)isoindolate

Phosphine-gold(I) derivatives of 1,1′-bis(alkynyl)metallocenes: Molecular structures of Fc’(CCX)2 [X = Au(PPh3), SiMe3] and Au4{(CC)2Fc’}2(PPh3)2 [Fc’ = Fe(η-C5H4-)2]

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