Cyclic and Linear Polyferrocenes with Silicon and Tin as Alternating Bridges

Bagh, Bidraha; Breit, Nora C.; Dey, Subhayan; Gilroy, Joe B.; Schatte, Gabriele; Harms, Klaus; Müller, Jens

doi:10.1002/chem.201200953

Cited by 14 publications

(17 citation statements)

References 116 publications

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“…The versatility of ROP is also evident from the numerous spacers that can be incorporated in the polymeric main chain through this technique. These spacers that include single atom spacers such as Si, [ 41,134,135,140,[148][149][150][151][152] P, [ 127,[153][154][155][156][157][158][159] B, [ 139,160 ] Sn, [ 141,152,161 ] S, [ 162 ] Ge, [ 125,163 ] Ga, [ 60,164 ] Al, [ 60 ] Se; [ 162 ] two-atom spacers such as C-C, [ 122,136,145,147 ] C-P, [ 129 ] C-Si, [ 129 ] C-S, [ 129 ] C-Ge, [ 165 ] C-Sn; [ 165 ] as well as a four-atom butadienylene spacer, [ 144 ] affect the properties of macromolecules. For instance, reaction of dilithioferrocene ( 90 ) with the gallium dichloride ( 91 ) yielded the strained gallium-bridged ferrocenophane ( 92 ), which spontaneously underwent ROP to afford the poly(ferrocenylgallane) ( 93 ) (Scheme 17 ).…”

Section: Macromolecules Bearing Sandwich Complexes In the Main Chainmentioning

confidence: 99%

Sandwich Complex‐Containing Macromolecules: Property Tunability Through Versatile Synthesis

Abd‐El‐Aziz

Agatemor

Etkin

2014

Macromol. Rapid Commun.

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Sandwich complexes feature unique properties as the physical and electronic properties of a hydrocarbon ligand or its derivative are integrated into the physical, electronic, magnetic, and optical properties of a metal. Incorporation of these complexes into macromolecules results in intriguing physical, electrical, and optical properties that were hitherto unknown in organic-based macromolecules. These properties are tunable through well-designed synthetic strategies. This review surveys many of the synthetic approaches that have resulted in tuning the properties of sandwich complex-containing macromolecules. While the past two decades have seen an ever-growing number of research publications in this field, gaps remain to be filled. Thus, we expect this review to stimulate research interest towards bridging these gaps, which include the insolubility of some of these macromolecules as well as expanding the scope of the sandwich complexes.

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Section: Macromolecules Bearing Sandwich Complexes In the Main Chainmentioning

confidence: 99%

Sandwich Complex‐Containing Macromolecules: Property Tunability Through Versatile Synthesis

Abd‐El‐Aziz

Agatemor

Etkin

2014

Macromol. Rapid Commun.

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“…17 Müller et al, in an attempt to synthesize [1.1]ferrocenophanes with alternating bridges of silicon and tin were able to prepare both cyclic and linear oligomers of up to 10 and 11 (respectively) repeating units of alternating ferrocenyl silanes and ferrocenyl stannanes of formulae [( 5 -C 5 H 4 )Fe( 5 -C 5 H 4 SiR 2 )-( 5 -C 5 H 4 )Fe( 5 -C 5 H 4 SnR' 2 )] n (R = Me and Et, R' = Me, n-Bu, and t-Bu). 22 There are four reported examples of polyferrocenylstannanes containing a single tin bridge. Due to the nature of tin, bulky substituents must be used to stabilize stannyl- [1]ferrocenophanes, which are able to undergo ROP.…”

Section: Introductionmentioning

confidence: 99%

Synthesis and characterization of a polyferrocenyldistannane

et al. 2014

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The distannyl-bridged poly bis(dimethylstannyl)ferrocene, 5, was synthesized through either the metal-catalyzed intermolecular dehydrogenative condensation of the bis(dimethylstannyl)ferrocene, 6, or the ring-opening polymerization of the distannane-bridged [2]ferrocenophane, 7. Both polymerization strategies yielded compounds displaying NMR ( 1 H, 13 C, 119 Sn) evidence for a distannane bridged polymer. A modest moderate molecular weight (GPC; M w = 9.5 × 10 4 Da, PDI = 1.76) was found for polymer 5 prepared by dehydrogenative condensation. Polymer 5 displayed electronic communication (≈ 0.2 V) between neighbouring iron centers, similar to those reported for monobridged ferrocenyl stannane polymers. Polymer 5 was further characterized by UV-vis spectroscopy, elemental analysis, and modeled with the related distannyl-8 and tristannyl-9 bisferrocenes using DFT at the SDD level of theory.Résumé : Le poly[bis(diméthylstannyl)ferrocène] distannyl-ponté, 5, a été synthétisé soit par condensation déshydrogénative intermoléculaire métallo-catalysée du bis(diméthylstannyl)ferrocène, 6, soit par polymérisation par ouverture de cycle du [2]ferrocénophane distannane-ponté, 7. Ces deux modes de polymérisation ont produit des composés dont l'analyse par RMN ( 1 H, 13 C, 119 Sn) a fourni les preuves de l'existence d'un polymère distannane-ponté. On a découvert que le poids moléculaire du polymère 5 produit par condensation déshydrogénative était modérément faible (résultats de la chromatographie par perméa-tion de gel (GPC) : M w = 9,5 × 10 4 Da et index de polydispersité (PDI) = 1.76). Le polymère 5 laisse apparaître des communications électroniques (≈ 0.2 V) entre centre ferriques voisins semblable à celles observées sur les polymères de polymères de ferrocényl stannane monopontés. Le polymère 5 a été caractérisé en détail par spectroscopie UV-visible et par analyse élémentaire et modelisé à l'aide des distanyl-(8) et tristannyl-(9) bisferrocènes en utilisant la théorie de la fonctionnelle de la densité (DFT) au niveau de théorie SDD. [Traduit par la Rédaction]

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“…Figure 1.17: Route to synthesis of alternating FcSnFcSi oligomers. R = Me, Et; R' = Me, n-Bu, t-BuMuller et al127 in an attempt to synthesis[1.1]ferrocenophanes with alternating bridges of…”

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confidence: 99%

Synthesis and characterization of ferrocenyl stannanes and polyferrocenyl stannanes

Ward¹

2021

Preprint

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A novel polymer polybis(dimethyl stannyl)ferrocene was synthesized through both metal catalyzed intermolecular dehydrogenative condensation and ring-opening polymerization. This polymer was the first evidence of a dibridged polyferrocenyl stannane, and was found to be of low to moderate molecular weight by gel permation chromatography and 1H NMR spectroscopy. This polymer displayed extensive electronic communication observed previously synthesized monobridged ferrocenyl stannane polymers. The first tristanna-bridged 3.3]ferrocenophane was discovered through an amine coupling of a tin amine, and 1,1’bis(dimethyl stannyl) ferrocene. The [3.3]ferrocenophane displayed a strong interaction between connected ferrocenes despite the large distance, (8.49 Å) between Fe centers. Finally, a new and improved synthesis of 1,1,2,2-tetramethyldistanna-[2]ferrocenophane was found. This metal catalyzed intramolecular dehydrogenative coupling employs Pd2(dba)3 as a catalyst and yields 90% product. All products were characterized where possible 1H, 13C, and 119Sn NMR and UV-Visible spectrocopy, as well as through cyclic voltammetry and DFT modeling.

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Cyclic and Linear Polyferrocenes with Silicon and Tin as Alternating Bridges

Cited by 14 publications

References 116 publications

Sandwich Complex‐Containing Macromolecules: Property Tunability Through Versatile Synthesis

Sandwich Complex‐Containing Macromolecules: Property Tunability Through Versatile Synthesis

Synthesis and characterization of a polyferrocenyldistannane

Synthesis and characterization of ferrocenyl stannanes and polyferrocenyl stannanes

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