Intervalence charge transfer across noncovalent interactions on vinyl silyl bridged biferrocenyl compounds

Montero‐Campillo, M. Merced; Bruña, Sonia; Cuadrado, Isabel; Mó, Otília

doi:10.1016/j.comptc.2014.08.005

Cited by 5 publications

(4 citation statements)

References 41 publications

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“…We obtain a vertical ionisation potential value of 6.08 eV for 5, in agreement with previous values for compounds 6 and 7 (6.16 and 6.08 eV). 27 The calculated UV-Vis spectrum of 5 in CH 2 Cl 2 along with the different orbital contributions to each transition is provided in Fig. S35 and Table S14 (see the ESI †).…”

Section: Electrochemistry and Electronic Structure Calculationsmentioning

confidence: 99%

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Formation of unexpected silicon- and disiloxane-bridged multiferrocenyl derivatives bearing Si–O–CHCH₂ and Si–(CH₂)₂C(CH₃)₃ substituents via cleavage of tetrahydrofuran and trapping of its ring fragments

et al. 2017

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The formation of a family of silicon- and siloxane-bridged multiferrocenyl derivatives carrying different functional groups attached to silicon, including Fc(CH)C(CH)SiCH[double bond, length as m-dash]CH (5), Fc(CH[double bond, length as m-dash]CH-O)SiCH[double bond, length as m-dash]CH (6), Fc(OH)SiCH[double bond, length as m-dash]CH (7), Fc(CH[double bond, length as m-dash]CH-O)Si-O-Si(O-CH[double bond, length as m-dash]CH)Fc (8) and Fc(CH[double bond, length as m-dash]CH-O)Si-O-SiFc (9) is described. Silyl vinyl ether molecules 6, 8 and 9 and the heteroleptic vinylsilane 5 resulted from the competing metathesis reaction of lithioferrocene (FcLi), CH[double bond, length as m-dash]CH-OLi or (CH)C(CH)Li with the corresponding multifunctional chlorosilane, ClSiCH[double bond, length as m-dash]CH or ClSi-O-SiCl. The last two organolithium species have been likely formed in situ by fragmentation of the tetrahydrofuran solvent. Diferrocenylvinyloxyvinylsilane 6 is noteworthy since it represents a rare example of a redox-active silyl mononomer in which two different C[double bond, length as m-dash]C polymerisable groups are directly connected to silicon. The molecular structures of the silicon-containing multiferrocenyl species 5, 6, 8 and 9 have been investigated by single-crystal X-ray diffraction studies, demonstrating the capture and storage processes of two ring fragments resulting from the cleavage of cyclic THF in redox-active and stable crystalline organometallic compounds. From electrochemical studies we found that by changing the anion of the supporting electrolyte from [PF] to [B(CF)], the redox behaviour of tetrametallic disiloxane 8 can be switched from a poorly resolved multistep redox process to four consecutive well-separated one-electron oxidations, corresponding to the sequential oxidation of the four ferrocenyl moieties.

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Section: Electrochemistry and Electronic Structure Calculationsmentioning

confidence: 99%

“…This compound exhibits slightly larger iron charge variations on their response to oxidation with respect to values reported for compounds 6 and 7 at the same level of theory. 27 Accordingly, spin densities on iron atoms in the radical species present values of 0.699 and 0.398 a.u.…”

Section: Electrochemistry and Electronic Structure Calculationsmentioning

confidence: 99%

Formation of unexpected silicon- and disiloxane-bridged multiferrocenyl derivatives bearing Si–O–CHCH₂ and Si–(CH₂)₂C(CH₃)₃ substituents via cleavage of tetrahydrofuran and trapping of its ring fragments

et al. 2017

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“…Furthermore, the study of electron transfer and electronic interactions within such structural motives has mainly been neglected 11. On the other hand, compounds in which two ferrocenyl termini are connected via a single atomic bridge, including C,16 N,17 O,18 Si,19,20 P,21 Hg,22 Sn,23 display interesting chemical and electrochemical properties. In addition, it has been demonstrated on the example of ferrocenyl functionalized pyrroles that the electronic characteristics of the bridge can be modified in a very controlled manner by electron‐withdrawing and electron‐donating functionalities at the nitrogen atom 24,25…”

Section: Introductionmentioning

confidence: 99%

Electronic Tuneable Dynamic and Electrochemical Behavior of N‐(Diferrocenylmethylene)anilines

Saloman

Hildebrandt

Korb

et al. 2015

Zeitschrift anorg allge chemie

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N-(Diferrocenylmethylene)anilines Fc 2 C=N-4-C 6 H 4 -R [3a R = CF 3 ; 3b R = Cl; 3c R = H; 3d R = CH 3 ; 3e R = OCH 3 ; Fc = Fe(η 5 -C 5 H 4 )(η 5 -C 5 H 5 )] with different electron-donating or -withdrawing functionalities were synthesized by a Schiff base reaction of substituted anilines H 2 N-4-C 6 H 4 -R (2a-2e) with diferrocenyl ketone (1). Within variable temperature NMR experiments activation enthalpies between 68.1 and 72.3 kJ·mol -1 for an E/Z exchange reaction of the imines were determined. It could be shown that the inversion barrier depends on the nature of the substituent R. Furthermore, electrochemical measurements were performed, demonstrating that the ferrocenyl units are oxidized separately. The electron density at the nitrogen

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“…Clearly, in agreement with the results obtained for 1 and the remarkable original studies reported by Geiger and co-workers, , the combination of CH 2 Cl 2 and [ n -Bu 4 N][B(C 6 F 5 ) 4 ] as solvent/electrolyte medium provides more favorable conditions for electrochemical studies of silicon-containing polyferrocenyl compounds, minimizing ion-pairing interactions between the [B(C 6 F 5 ) 4 ] − electrolyte anion and the cationic products generated in the oxidation processes. In addition, the presence of two separated oxidation processes, both with [PF 6 ] − and [B(C 6 F 5 ) 4 ] − electrolyte anions, suggests the existence of appreciable iron–iron electronic interactions between the two neighboring ferrocenyl units linked to different silicon atoms, in the disiloxane Si–O–Si moiety. , …”

Section: Resultsmentioning

confidence: 99%

Ferrocene and Silicon-Containing Oxathiacrown Macrocycles and Linear Oligo-Oxathioethers Obtained via Thiol–Ene Chemistry of a Redox-Active Bifunctional Vinyldisiloxane

et al. 2015

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The application of 1,3-divinyl-1,3-dimethyl-1,3-diferrocenyldisiloxane [(CH 2 CH)FcMeSi] 2 O (1) as an efficient electroactive vinylsilane precursor for thiol−ene radical reactions is described. In order to determine if steric or electronic limitations due to the redox-active metallocene moiety might affect the bis(hydrothiolation) of the bifunctional vinylsilane, a model reaction was initially performed between 1 and 2-mercaptoethanol, resulting in the formation of the newly sulfur-containing carbosiloxane 2 in excellent yield. The bis(thiol−ene) reaction of 1 was successfully extended to 2,2′-(ethylenedioxy)diethanethiol, affording a series of novel precisely defined, redox-active oxathiacrown macrocycles (3 and 4 n ) and sulfur-bearing linear oligo-carbosiloxanes (5 n and 6 n ) with a backbone in which the −S(CH 2 ) 2 −O(CH 2 ) 2 O−(CH 2 ) 2 S− chain and the −Si−O−Si− bond, bearing pendant ferrocenes, are alternately linked by ethylene bridges. These reactions have been initiated either thermally (in toluene solution with AIBN) or by UV light irradiation in THF in the presence of 2,2-dimethoxy-2-phenylacetophenone (DMPA) as photoinitiator, even though UV photoinitiated thiol−ene reactions were found to be the most efficient hydrothiolations. All newly silicon-containing oxathioether-based ferrocenyl compounds 2−6 n have been thoroughly characterized using a combination of elemental analysis, multinuclear NMR spectroscopy, FT-IR, and MALDI-TOF mass spectrometry to establish their chemical structures and chain-end functionalities. The electrochemical behavior of 2−6 n has been examined by cyclic and square wave voltammetries, in dichloromethane solution using [PF 6 ] − and [B(C 6 F 5 ) 4 ] − as supporting electrolyte anions of different coordinating ability. The sulfur-rich cyclic and linear oligomers 4 n −6 n exhibit excellent chemisorption properties and spontaneously form robustly adsorbed electroactive films onto Au or Pt electrode surfaces. The cation complexation ability of diferrocenyl silaoxathiacrown ether 3 has been studied using electrochemical and 1 H NMR spectroscopic techniques. The voltammetric behavior of receptor 3 has proved to be very sensitive to the presence of Hg 2+ cation. The ability of macrocycle 3 to bind Hg 2+ has also been investigated through electronic structure calculations, being the interaction between the cation and one of the cyclopentadienyl rings the responsible of the different behavior of both redox-active centers.

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Intervalence charge transfer across noncovalent interactions on vinyl silyl bridged biferrocenyl compounds

Cited by 5 publications

References 41 publications

Formation of unexpected silicon- and disiloxane-bridged multiferrocenyl derivatives bearing Si–O–CHCH₂ and Si–(CH₂)₂C(CH₃)₃ substituents via cleavage of tetrahydrofuran and trapping of its ring fragments

Formation of unexpected silicon- and disiloxane-bridged multiferrocenyl derivatives bearing Si–O–CHCH₂ and Si–(CH₂)₂C(CH₃)₃ substituents via cleavage of tetrahydrofuran and trapping of its ring fragments

Electronic Tuneable Dynamic and Electrochemical Behavior of N‐(Diferrocenylmethylene)anilines

Ferrocene and Silicon-Containing Oxathiacrown Macrocycles and Linear Oligo-Oxathioethers Obtained via Thiol–Ene Chemistry of a Redox-Active Bifunctional Vinyldisiloxane

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Intervalence charge transfer across noncovalent interactions on vinyl silyl bridged biferrocenyl compounds

Cited by 5 publications

References 41 publications

Formation of unexpected silicon- and disiloxane-bridged multiferrocenyl derivatives bearing Si–O–CHCH2 and Si–(CH2)2C(CH3)3 substituents via cleavage of tetrahydrofuran and trapping of its ring fragments

Formation of unexpected silicon- and disiloxane-bridged multiferrocenyl derivatives bearing Si–O–CHCH2 and Si–(CH2)2C(CH3)3 substituents via cleavage of tetrahydrofuran and trapping of its ring fragments

Electronic Tuneable Dynamic and Electrochemical Behavior of N‐(Diferrocenylmethylene)anilines

Ferrocene and Silicon-Containing Oxathiacrown Macrocycles and Linear Oligo-Oxathioethers Obtained via Thiol–Ene Chemistry of a Redox-Active Bifunctional Vinyldisiloxane

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Formation of unexpected silicon- and disiloxane-bridged multiferrocenyl derivatives bearing Si–O–CHCH₂ and Si–(CH₂)₂C(CH₃)₃ substituents via cleavage of tetrahydrofuran and trapping of its ring fragments

Formation of unexpected silicon- and disiloxane-bridged multiferrocenyl derivatives bearing Si–O–CHCH₂ and Si–(CH₂)₂C(CH₃)₃ substituents via cleavage of tetrahydrofuran and trapping of its ring fragments