Conformationally Modulated Intramolecular Electron Transfer Process in a Diaza[2,2]ferrocenophane

Otón, Francisco; Ratera, Imma; Espinosa, Arturo; Tárraga, Alberto; Veciana, Jaume; Molina, Pedro

doi:10.1021/ic902059y

Cited by 48 publications

(43 citation statements)

References 33 publications

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“…Interestingly, ethynylferrocene ( 1 ) readily undergoes copper(I)-catalyzed 1,3-dipolar cycloaddition reactions with azides (the CuAAC reaction), yielding ferrocene-containing 1,2,3-triazole derivatives. − Indeed, the CuAAC alkyne–azide reaction has recently emerged as an easy and popular synthetic method, as it falls into the category of click chemistry due to its high regioselectivity and efficiency, mild conditions, and simple product isolation . This particular reaction involving ethynylferrocene has been successfully applied, over the past few years, to the synthesis of ferrocenyl-containing polymers and dendrimers as well as ferrocene-based redox sensors for anions and metal cations. , …”

Section: Introductionmentioning

confidence: 99%

Efficient Thiol–Yne Click Chemistry of Redox-Active Ethynylferrocene

et al. 2014

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The application of ethynylferrocene, FcCCH (1), as a highly efficient electroactive precursor for the thiol–yne click reaction is presented. For this purpose, a wide range of functionalized thiols, namely 2-mercaptoethanol, 1-thioglycerol, 3-mercaptopropionic acid, 4-aminothiophenol, and benzene-1,3-dithiol as well as tetrathiol pentaerythritol tetrakis(3-mercaptopropionate), were investigated. This facile thiol–ethynylferrocene radical reaction has resulted in the quantitative formation and isolation of the newly ferrocenyl–vinyl sulfides FcCHCHS(CH2)2OH (2 Z and 2 E ), FcCHCHSCH2CH(OH)CH2OH (3 Z and 3 E ), FcCHCHS(CH2)2COOH (4 Z and 4 E ), FcC(CH2)S(1,4-C6H4)NH2 (5α), FcCHCHS(1,3-C6H4)SCHCHFc (6), and [FcCHCHS(CH2)2COOCH2]4C (7). Thiol–ethynylferrocene reactions have been initiated either by heat, in toluene with AIBN, or by UV light irradiation in THF in the presence of DMPA as photoinitiator. The outcome of the hydrothiolation of ethynylferrocene strongly depends on the thiol structure and on the initiation method employed. A simple mixing of metallocene 1 with the thiol HS(CH2)2OH or HS(CH2)2COOH in a proper ratio, in THF at 20 °C, in a initiator-free thiol–yne reaction, causes hydrothiolation of 1 to occur, allowing for the formation of vinyl sulfides 2 Z , 2 E and 4 Z , 4 E in good isolated yields. In contrast to the bis-addition typically observed for thiol–yne reactions, no double hydrothiolation to FcCCH has been observed for any of the thiols under any conditions studied. Electrochemical studies showed that tetrametallic compound 7, containing four sulfur-bridged ferrocenyl–vinyl moieties, behaves as a tetrapodal adsorbate molecule, exhibiting excellent chemisorption properties, and spontaneously forms robustly adsorbed 7 films onto Au or Pt electrode surfaces.

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Section: Introductionmentioning

confidence: 99%

Efficient Thiol–Yne Click Chemistry of Redox-Active Ethynylferrocene

et al. 2014

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“…Such multiple charge transfer transitions originate from multiple ligand-mediated orbital interactions and level splitting through low symmetry and spin–orbit coupling . For instance, a diaza[2.2]ferrocenophane complex displays two IVCT bands attributable to two stable atropo isomers in poor polar solvents . Due to the strong spin–orbit coupling effect of the osmium atom, the number of IVCT bands could be up to five in binuclear osmium mixed-valence complexes .…”

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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“…Although the related N , N ′-diferrocenylcarbodiimide was reported as early as 1966, to the best of our knowledge the 1,1′-dicarbodiimidoferrocenes (Figure , I) have never been employed as pro ligands in coordination chemistry. Of related interest [3.3]-ferrocenophanes and the 2,4-diimino-1,3-azetidines have been exploited for ion sensing by various spectroscopic (NMR, UV–vis) and electrochemical means. − More recently these kinds of ferrocenophanes have been used as supporting structures for hosting diradicals. , Carbodiimides (Figure , II) themselves find uses as pro ligands in inorganic chemistry due to their ability to bind a wide range of elements including the p-block elements (e.g., amidinato sylilenes and heavier congeners, likewise for boron) as tight bite angle supporting ligands in the form of amidinates (Figure , III) and the closely related guanidinates (Figure , IV). , …”

Section: Introductionmentioning

confidence: 99%

1,1′-Dicarbodiimidoferrocenes: Synthesis, Characterization, and Group IV 1,1′-Bisguanidinateferrocene Complexes

Palomero

Jones

2019

Organometallics

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We report the two-step one-pot preparation of a series of bulky substituted 1,1′-dicarbodiimidoferrocene proligands. In solution the compounds achieve equilibrium with the corresponding 2,4-diimino-1,3azetidine products which exhibit distinct spectroscopic and electrochemical features. Metalation of the carbodiimides with M(NMe 2 ) 4 (M = Zr, Hf) leads to fluxional six-coordinate compounds that exhibit intermediate Bailar twist features in solution and in the solid state. Coordination of the 2,4-diimino-1,3-diazetidines to Zr(NMe 2 ) 4 results in a metal-mediated carbodiimide metathesis into two zirconium guanidinate complexes, which can be rationalized by a two-step reaction mechanism.

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Conformationally Modulated Intramolecular Electron Transfer Process in a Diaza[2,2]ferrocenophane

Cited by 48 publications

References 33 publications

Efficient Thiol–Yne Click Chemistry of Redox-Active Ethynylferrocene

Efficient Thiol–Yne Click Chemistry of Redox-Active Ethynylferrocene

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

1,1′-Dicarbodiimidoferrocenes: Synthesis, Characterization, and Group IV 1,1′-Bisguanidinateferrocene Complexes

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