Anorganische Ringsysteme mit Ferrocenyl‐Substituenten
TL;DR: In this paper, a ring system containing Ferrocenyl Substituents is synthesized starting from FcPCl2 (1, FcPH2 (2), FcAsCl2(3) and Fe(C5H4A6H2)2 (4), which contains an eight-membered As2S2N4 ring.
Abstract: Ausgehend von FcPCl2 (1), FcPH2 (2), FcAsCl2 (3) und Fe(C5H4AsCl2)2 (4) werden drei-, vier-, funf- und achtgliedrige Heterocyclen mit Ferrocenyl-Substitutenten synthetisiert (Fc = Ferrocenyl). Durch Umsetzung von 1 mit 2 in Gegenwart von DBU entsteht (FcP)n, das mit (Ph3P)2Pt(C2H4) zu (7) reagiert. Der analoge As2Pt-Ring 9 ist uber (FcAs)3 (8) in guter Ausbeute zuganglich. Die Reduktion von 1 mit LiAlH4 liefert (FcP)4 (10). Ein funfgliedriger Arsen-Schwefel-Heterocyclus, Fc2As2S3 (12), entsteht durch Umsetzung von FcAs=P(2,4,6-tBu3C6H2) (11) mit Schwefel. FcAsCl2 (3) reagiert mit Me3SiNSNSiMe3 zu FcAs(NSN)2AsFc (13), das einen achtgliedrigen As2S2N4-Ring enthalt. Dessen Komplexierung mit (Norbornadien)M(CO)4 fuhrt zu den Tetracarbonyl-Komplexen [FcAs(NSN)2AsFc]M(CO)4 (14, 15; M = Cr, Mo). Ein Arsenuberbrucktes Ferrocenophan 16 kann bei der Reaktion von Fe(C5H4Li)2 × TMEDA mit AsCl3 isoliert werden. Auch die Umsetzung von 4 mit Me3SiNSNSiMe3 liefert ein kondensiertes Ferrocenophan-Derivat der Zusammensetzung (C5H4)2FeAs2N6S4 (17). Die Molekulstrukturen von 13 und 17 wurden rontgenographisch bestimmt.
Inorganic Ring System Containing Ferrocenyl Substituents
Three-, four-, five-, and eight-membered heterocycles are synthesized starting from FcPCl2 (1), FcPH2 (2), FcAsCl2 (3) and Fe(C5H4AsCl2)2 (4) (Fc = Ferrocenyl). Treatment of 1 with 2 in the presence of DBU yields (FcP)n, which reacts with (Ph3P)2Pt(C2H4) to give (7). The corresponding As2Pt ring system 9 is available in high yield via (FcAs)3 (8). The reduction of 1 with LiAlH4 yields (FcP)4 (10). A five-membered arsenic sulfur heterocycle, Fc2As2S3 (12), is formed in the reaction of FcAs=P(2,4,6-tBu3C6H2) (11) with sulfur. FcAsCl2 (3) reacts with Me3SiNSNSiMe3 to give FcAs(NSN)2AsFc (13), which contains an eight-membered As2S2N4 ring. Its complexation with (norbornadiene)M(CO)4 leads to the tetracarbonyl complexes [FcAs(NSN)2AsFc]M(CO)4 (14, 15; M = Cr, Mo). An arsenic-bridged ferrocenophane 16 can be isolated from the reaction of Fe(C5H4Li)2 x TMEDA with AsCl3. The reaction of 4 with Me3SiNSNSiMe3 also produces a condensed ferrocenophane derivative, (C5H4)2FeAs2N6S4 (17). The molecular structures of 13 and 17 have been determined by X-ray diffraction.
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TL;DR: The 1,1′-dilithioferrocene can be used in situ, or when isolated as the pyrophoric adduct [(C 5 H 4 Li) 2 Fe]·TMEDA, to prepare the following complexes in high yields: ferrocene-1, 1, 1′-bis(dimethylarsine) (Fdma), ferrocenophane, Fdpa, Fdt, Fydioxene, and Fdmp, which can be converted quantitatively to Fdt by reduction with lithium aluminum hydr
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TL;DR: MetMetallocenophanes as discussed by the authors are metallocenes in which the cyclopentadienyl ligands are linked intramolecularly through CmHn or Cm HnX (X = heteroatom) chains.
Abstract: Metallocenophanes are metallocenes in which the cyclopentadienyl ligands are linked intramolecularly through CmHn or CmHnX (X = heteroatom) chains. Two main classes of metallocenophanes are known: in [m]metallocenophanes the ligands of one metallocene are connected by a bridge (or by several bridges); in [m.n]metallocenophanes two (or more) metallocenes are brought together into one molecule by bridging groups. This article briefly describes the first class (mononuclear complexes) and then concentrates on the second (binuclear complexes). The [1.1]metallocenophanes, which are produced by linking two metallocene moieties through two C1, bridges, are of particular interest and are characterized by a variety of unusual and useful properties: they are very flexible conformationally; hydride abstraction from the CH2 bridges produces carbenium ions that are greatly stabilized by the adjacent metallocene moieties; deprotonation of one of the CH2 bridges is surprisingly easy and leads to the unusual situation that an intramolecular CHċC hydrogen bond stabilizes a carbanion; protonation of both metallocene moieties causes the liberation of one mole of hydrogen per mole of [1.1]metallocenophane, thereby allowing the use of these compounds as catalysts for the formation of hydrogen in acidic aqueous solutions.
136 citations