Synthesis, structures and comparative electrochemical study of 2,5-bis(trimethylsilylethynyl)thiophene coordinated cobalt carbonyl units

Arnanz, Avelina; Marcos, M.L.; Moreno, C.; Farrar, David H.; Lough, Allan J.; Yu, Joanne O.; Delgado, Salomé; González‐Velasco, J.

doi:10.1016/j.jorganchem.2004.07.028

Cited by 15 publications

(22 citation statements)

References 72 publications

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“…Within the broad range of bridging ligands examined within [L n M(µ‐bridge)ML n ] + complexes, thiophene derivatives have attracted attention,, with the lower aromaticity of the heterocyclic ring in comparison with benzene thought likely to lead to increased contributions from a cumulene‐like ground state and more extensively delocalised electronic structures , . For example, Lapinte and Lo Sterzo and their respective co‐workers have reported that 2,5‐diethynylthiophene‐linked Fe(dppe)Cp* and Fe(dppe)Cp [Cp = cyclopentadienyl, Cp* = pentamethylpentadienyl, dppe = 1,2‐bis(diphenylphosphino)ethane] termini are more strongly coupled than the 1,4‐diethynylbenzene‐bridged analogues , .…”

Section: Introductionmentioning

confidence: 99%

Electronic Structures of Divinylchalcogenophene‐Bridged Biruthenium Complexes: Exploring Trends from O to Te

et al. 2017

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An homologous series of divinylchalcogenophene‐bridged binuclear ruthenium complexes [{(PMe3)3Cl(CO)Ru}2(µ‐CH=CH‐C4H2E‐CH=CH)] (4a–4d, E = O, S, Se, Te) have been synthesised and fully characterised by X‐ray crystallography and various spectroscopic techniques. The single‐crystal X‐ray diffraction results reveal a distinct short/long bond‐length alternation along the polyene‐like hydrocarbon backbone, with geometric constraints imposed by the chalcogenophene leading to an increasing distance between the two metal centres (dRu–Ru) in complexes 4a–4d as the heteroatom in the five‐membered ring is changed from oxygen (9.980 Å in 4a) to tellurium (11.063 Å in 4d). The complexes undergo two sequential one‐electron oxidation processes, the half‐wave potential and separation of which appear to be sensitive to a range of factors, including aromatic stabilisation and re‐organisation energies. Analysis of [4a–4d]n+ (n = 0, 1, 2) by UV/Vis/NIR and IR spectroelectrochemical methods, supported by DFT calculations (n = 0, 1), revealed that the redox character of the complexes is dominated by the polyene‐like backbone with the chalcogenide playing a subtle but influential, structural rather than electronic, role. In the radical cations [4a–4d]+, the charge is rather effectively delocalised over the 10‐atom Ru–[4‐s‐cis‐all‐trans‐(CH=CH)4]–Ru chain, giving rise to a species with spectroscopic properties not dissimilar to oxidised polyaceylene.

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Section: Introductionmentioning

confidence: 99%

Electronic Structures of Divinylchalcogenophene‐Bridged Biruthenium Complexes: Exploring Trends from O to Te

et al. 2017

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“…These absorptions have also been observed at similar values in the parent complexes 1, 2 and 3. 9,12 In addition, 1, 2 and 4-6 (containing uncomplexed C∫C triple bonds) exhibit a n C∫C very weak band (it could not be observed in 3). As expected, the n C∫C values of 1 and 2 (ca.…”

Section: Synthesis and Spectroscopic Characterizationmentioning

confidence: 98%

“…In the 13 C NMR spectra of 4, 5 and 7, the carbon resonances of the free and coordinated acetylene carbon atoms can be assigned on the basis of the chemical shifts, 13 C NMR spectra of 1 and 2, 9 NMR bidimensional experiments recorded (HMBC and HMQC) and by comparison with analogous complexes. 9,10,12,15,16 For 4, 5 and 7, the 13 C NMR spectra also confirm the equivalence of the two thiophene rings for each compound, showing four resonances due to the thiophene carbon atoms between 120 and 154 ppm.…”

Section: Synthesis and Spectroscopic Characterizationmentioning

confidence: 99%

“…3) have been previously prepared by reaction of their parent complexes with Bu 4 NF in THF/MeOH (10 : 1) or with a saturated solution of KOH in degassed methanol. 9,12 The oxidative coupling of 1, 2 and 3, using standard Eglinton-Glaser coupling conditions, 13 proceeded without difficulty to afford the stable complexes 4, 5 and 6, respectively (Schemes 1 and 2). All these compounds have been characterized by analytical and spectroscopic data (IR, UV-Vis, 1 H, 1 H{ 31 P}, 13 C{ 1 H}, 31 P{ 1 H} NMR and MS), details of which are given in the Experimental section and in Tables 1 and 2.…”

Section: Introductionmentioning

confidence: 99%

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Electronic communication through a poly-yne carbonyldicobalt complex containing an open linear triosmium cluster

et al. 2009

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The oxidative coupling of 2-[Co(2)(CO)(4)(micro-X){micro(2)-eta(2)-(SiMe(3)C(2))}]-5-(C[triple bond]CH)C(4)H(2)S (X = dppa (1), dppm (2)) and 3-[Co(2)(CO)(4)(micro-dmpm){micro(2)-eta(2)-(SiMe(3)C(2))}]-4-(C[triple bond]CH)C(4)H(2)S (3) using standard Eglinton-Glaser conditions yielded 2,2'-[Co(2)(CO)(4)(micro-X){micro(2)-eta(2)-(SiMe(3)C(2))}C(4)H(2)S](2)-5,5'-(C[triple bond]C)(2) (X = dppa (4), dppm (5)) and 3,3'-[Co(2)(CO)(4)(micro-dmpm){micro(2)-eta(2)-(SiMe(3)C(2))}C(4)H(2)S](2)-4,4'-(C[triple bond]C)(2) (6), respectively (dppa = (Ph(2)P)(2)NH; dmpm = (Me(2)P)(2)CH(2); dppm = (Ph(2)P)(2)CH(2)). The reaction of 5 with [Os(3)(CO)(11)(CH(3)CN)] afforded 2,2'-[Co(2)(CO)(4)(micro-dppm){micro(2)-eta(2)-(SiMe(3)C(2))}C(4)H(2)S](2)-5,5'-[Os(3)(CO)(11)(micro(3)-eta(4)-(C[triple bond]C)(2)] (7), where the triosmium cluster is open and coordinated as a linear chain to both triple bonds. The electrochemical study of 7 shows that the "Os(3)" unit significantly enhances the electronic communication between the "Co(2)" redox centres as compared with 5. Complex 6 was characterized by single-crystal X-ray diffraction analyses.

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“…Interpolation of other -conjugated moieties between the cluster centres gives rise to less strongly coupled to decoupled systems [48][49][50], with results from electrochemical studies being consistent with a significant contributions from both through-space and through-bond effects to the stabilisation of the one-electron redox products in some cases [51].…”

Section: Introductionmentioning

confidence: 98%

Synthesis, Structure and Electrochemical Properties of Triarylamine Bridged Dicobaltdicarbon Tetrahedrane Clusters

et al. 2012

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. (2012) 'Synthesis, structure and electrochemical properties of triarylamine bridged dicobaltdicarbon tetrahedrane clusters.', Journal of custer science., 23 (3). 853-872 . Further information on publisher's website:http://dx.doi.org/10.1007/s10876-012-0482-y Publisher's copyright statement:The original publication is available at www.springerlink.com Additional information: Use policyThe full-text may be used and/or reproduced, and given to third parties in any format or medium, without prior permission or charge, for personal research or study, educational, or not-for-prot purposes provided that:• a full bibliographic reference is made to the original source • a link is made to the metadata record in DRO • the full-text is not changed in any way The full-text must not be sold in any format or medium without the formal permission of the copyright holders.Please consult the full DRO policy for further details. AbstractThe reaction of [Co 2 (CO) 6 (dppm)] (1) + with respect to disproportionation can be attributed to electrostatic effects.

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Synthesis, structures and comparative electrochemical study of 2,5-bis(trimethylsilylethynyl)thiophene coordinated cobalt carbonyl units

Cited by 15 publications

References 72 publications

Electronic Structures of Divinylchalcogenophene‐Bridged Biruthenium Complexes: Exploring Trends from O to Te

Electronic Structures of Divinylchalcogenophene‐Bridged Biruthenium Complexes: Exploring Trends from O to Te

Electronic communication through a poly-yne carbonyldicobalt complex containing an open linear triosmium cluster

Synthesis, Structure and Electrochemical Properties of Triarylamine Bridged Dicobaltdicarbon Tetrahedrane Clusters

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