Synthese und Struktur des ersten [1]Ferrocenophans mit Schwefel als Brückenatom

Pudelski, John K.; Gates, Derek P.; Rulkens, Ron; Lough, Alan J.; Manners, Ian

doi:10.1002/ange.19951071335

Cited by 34 publications

(13 citation statements)

References 29 publications

(1 reference statement)

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“…Low solubilities of metallopolymers are a serious problem. For example, boron- [24,25] and sulfur-bridged [27][28][29] [1]FCPs, which are the most strained sandwich compounds known to date, polymerize thermally to give insoluble polymers. [33] 6) Living ROP with a perfect control over the molecular weight requires monomers of high purity.…”

Section: Resultsmentioning

confidence: 99%

“…Interestingly, the exothermy of the ROP measured by differential scanning calorimetry (DSC) was À95 kJ mol À1 [(Me 3 Si) 2 NBfc] and significantly lower than that of the similarly tilted sulfur-bridged [1]FCP (a = 31.05(10)8; DH ROP = À130A C H T U N G T R E N N U N G (AE20) kJ mol À1 ). [27][28][29] The lower than expected enthalpy was attributed to the destabilizing effect of the bulky amino group on the formed polymer. [25] Since this report appeared in 2000, no additional results about improved boron-bridged [1]FCPs have been published.…”

Section: Silicon-and Tin-bridged [1]fcps 4 B and 4 Cmentioning

confidence: 97%

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A Flexible Approach to Strained Sandwich Compounds: Chiral [1]Ferrocenophanes with Boron, Gallium, Silicon, and Tin in Bridging Positions

Sadeh¹,

Schatte²,

Müller³

2013

Chemistry A European J

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The enantiomerically pure dibromoferrocene 3 [(Sp,Sp )-1,1'-dibromo-2,2'-di(isopropyl)ferrocene], equipped with two iPr groups in α positions, was prepared using known "Ugi amine" chemistry. Species 3 was targeted in order to gain access to new [1]ferrocenophanes ([1]FCPs) to be used as monomers for ring-opening polymerization. The iPr groups on the sandwich unit were introduced to stabilize bridging moieties, as well as to increase solubilities of targeted metallopolymers. The planar chiral dibromide 3 can quantitatively be lithiated at 0°C [2 equiv nBuLi, hexanes/thf (9:1), 30 min]. Salt-metathesis reactions with respective element dichloride species gave chiral [1]FCPs with a variety of bridging moieties [ERx =Ga[2-(Me2NCH2)C6H4] (4 a), SiMe2 (4 b), SntBu2 (4 c), BNiPr2 (4 d)]. The new [1]FCPs were fully characterized including single-crystal X-ray analysis. The stabilizing iPr groups on the Cp rings increase the thermal stabilities of 4 b-d compared to known [1]FCPs, equipped with the same bridging moieties. All three compounds 4 b-d are volatile and could be isolated by vacuum sublimation. Our new approach to [1]FCPs has the potential to overcome many of the existing difficulties in ferrocenophane chemistry, such as limited stability of starting monomers and low solubilities of resulting polyferrocenes.

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Section: Resultsmentioning

confidence: 99%

Section: Silicon-and Tin-bridged [1]fcps 4 B and 4 Cmentioning

confidence: 97%

A Flexible Approach to Strained Sandwich Compounds: Chiral [1]Ferrocenophanes with Boron, Gallium, Silicon, and Tin in Bridging Positions

Sadeh¹,

Schatte²,

Müller³

2013

Chemistry A European J

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“…(13)]. 124 Die schwefel‐ und selenverbrückten [1]Ferrocenophane 33 bzw. 34 sind durch typische Salzmetathesen ausgehend von Dilithioferrocen zugänglich, wenn die Aufarbeitung bei tiefen Temperaturen erfolgt 24.…”

Section: Metallorganische Ringe Mit Zwei Cyclopentadienylliganden:unclassified

Gespannte Metallocenophane und ähnliche metallorganische Ringe mit π‐Kohlenwasserstoffliganden und Übergangsmetallzentren

2007

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Die Strukturen, Bindungsverhältnisse und Ringöffnungsreaktionen gespannter cyclischer Kohlenstoffverbindungen sind ein fester Bestandteil des Lehrbuchwissens. Gespannte metallorganische Verbindungen mit Übergangsmetallzentren blicken hingegen auf eine viel kürzere Geschichte zurück: Erst jüngere Arbeiten zu ihrer Synthese und ihren Eigenschaften deckten faszinierende Aspekte ihrer Struktur, Bindungsverhältnisse und Reaktivität auf. Auf der Grundlage der Untersuchungen zu gespannten Ferrocenophanen wurden vielfältige gespannte metallorganische Ringe mit unterschiedlichen Metallzentren, π‐Kohlenwasserstoffliganden und Brücken entwickelt. Solche gespannten Spezies können unter Ringöffnung an Oberflächen binden (und diese funktionalisieren) oder durch Ringöffnungspolymerisationen leicht verarbeitbare Metallopolymere bilden. Dieser Aufsatz fasst den aktuellen Stand der Synthese und Strukturbestimmung sowie die Kenntnisse über die elektronische Struktur und die Reaktivität gespannter metallorganischer Ringe mit π‐Kohlenwasserstoffliganden und d‐Block‐Metallen zusammen.

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“…[61] Photochemical reaction of 1 with [Fe(CO) 5 ] in THF: Compound 1 (35 mg, 0.096 mmol) was dissolved in THF (4 mL). The resulting orange solution was then transferred to a Schlenk tube.…”

Section: Synthesis Ofmentioning

confidence: 99%

“…[12] Compound 11 is presumably formed by insertion of a photochemically generated [Fe(CO) 4 ] fragment into the Fe À Cp bond, followed by rearrangement of the carbonyl ligands. The insertion of the [Fe(CO) 4 ] moiety between the Cp rings dramatically increases the C(1A)-S(1)-C(1) angle in 11 (100.76 (17) o ) from the corresponding angle in 8 (89.03 (9) o ) [61] Compared to analogous structures, cis- [62] and [Fe 2 (CO) 2 …”

mentioning

confidence: 96%

Photoinduced FeCp Bond Cleavage and Insertion Reactions of Strained Silicon‐ and Sulphur‐Bridged [1]Ferrocenophanes in the Presence of Transition‐Metal Carbonyls

Ieong

Chan

Lough

et al. 2008

Chemistry A European J

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The photochemical reactions of the moderately strained sila[1]ferrocenophane [Fe(eta-C(5)H(4))(2)SiPh(2)] (1) and the highly strained thia[1]ferrocenophane [Fe(eta-C(5)H(4))(2)S] (8) with transition-metal carbonyls ([Fe(CO)(5)], [Fe(2)(CO)(9)] and [Co(2)(CO)(8)]) have been studied. The use of metal carbonyls has allowed the products of photochemically induced Fe-cyclopentadienyl (Cp) bond cleavage reactions in the [1]ferrocenophanes to be trapped as stable, characterisable products. During the course of these studies the synthesis of 8 from [Fe(eta-C(5)H(4)Li)(2)TMEDA] (TMEDA=N,N,N',N'-tetramethylethylenediamine) and S(SO(2)Ph)(2) has been significantly improved by a change of reaction solvent and temperature. Photochemical reaction of 1 with excess [Fe(CO)(5)] in THF gave the dinuclear complex [Fe(2)(CO)(2)(mu-CO)(2)(eta-C(5)H(4))(2)SiPh(2)] (9). The analogous photolytic reaction of 8 with [Fe(CO)(5)] in THF gave cyclic dimer [Fe(eta-C(5)H(4))(2)S](2) (10) and [Fe(2)(CO)(2)(mu-CO)(2)(eta-C(5)H(4))(2)S] (11), with the former being the major product. Photolysis of 1 with [Co(2)(CO)(8)] afforded the remarkable tetrametallic dimer [(CO)(2)Co(eta-C(5)H(4))SiPh(2)(eta-C(5)H(4))Fe(CO)(2)](2) (13). The corresponding photochemical reaction of 8 with [Co(2)(CO)(8)] gave a trimetallic insertion product in high conversion, [Co(CO)(4)(CO)(2)Fe(eta-C(5)H(4))S(eta-C(5)H(4))Co(CO)(2)] (14). These reactivity studies show that UV light promotes Fe-Cp bond cleavage reactions of both of the [1]ferrocenophanes 1 and 8. We have found that, whereas the less strained sila[1]ferrocenophane 1 requires photoactivation for Fe-Cp bond insertions to occur, the highly strained thia[1]ferrocenophane 8 undergoes both irradiative and non-irradiative insertions, although the latter occur at a slower rate. Our results suggest that such photoinduced bond cleavage reactions may be general and applicable to other related strained organometallic rings with pi-hydrocarbon ligands.

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Synthese und Struktur des ersten [1]Ferrocenophans mit Schwefel als Brückenatom

Cited by 34 publications

References 29 publications

A Flexible Approach to Strained Sandwich Compounds: Chiral [1]Ferrocenophanes with Boron, Gallium, Silicon, and Tin in Bridging Positions

A Flexible Approach to Strained Sandwich Compounds: Chiral [1]Ferrocenophanes with Boron, Gallium, Silicon, and Tin in Bridging Positions

Gespannte Metallocenophane und ähnliche metallorganische Ringe mit π‐Kohlenwasserstoffliganden und Übergangsmetallzentren

Photoinduced FeCp Bond Cleavage and Insertion Reactions of Strained Silicon‐ and Sulphur‐Bridged [1]Ferrocenophanes in the Presence of Transition‐Metal Carbonyls

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