A Synthetic Route to Borylene‐Bridged Poly(ferrocenylene)s

Abstract

Iron chains: The highly soluble, ferrocene‐containing polymer [‐fc‐B(Mes)‐]n (fc=Fe(C5H4)2, Mes=mesityl), with an average chain length of about 16 repeat units (n=16), is readily accessible by a novel polycondensation reaction starting from fc(BBr2)2 and HSiEt3 (see scheme). The polymer contains three‐coordinate boron centers, which are well‐suited for the promotion of electron delocalization along the polymer chain.

Alternative synthesis and crystal structure of a [2]boraferrocenophane

“…These compounds have attracted considerable interest [10,11], since corresponding [1]borazirconocenophanes constitute active catalysts for the polymerization of olefins [1][2][3][4][5]12] and the highly strained [1]boraferrocenophanes proved their propensity to undergo ring-opening polymerization yielding poly(ferrocenyl)boranes [8,9,13]. Two different routes have been applied to the synthesis of these complexes.…”

Recent Advances in the Synthesis and Applications of Organoborane Polymers

“…In addition, Sonogashira-Hagihara coupling was used to embed bis(borabenzene)iron complexes into conjugated polymers (24, Scheme 5c), while a recent report details the Stille-type polymerization of thiophene derivatives of diboraanthracene [102]. Other less frequently employed techniques include the spontaneous polymerization of in situ generated ferrocenylboranes, H(Br)B-fc-B(Br)H (fc ¼ 1,1 0 -ferrocenediyl) (25, Scheme 5d) [103], the spontaneous ring-opening polymerization of borafluorenes [104], and the use of preformed organoboranes in click reactions [105]. Electropolymerization presents yet another alternative; however, its use has been largely limited to monomers with boronic ester or carborane pendant groups.…”

Funktionelle polymere Materialien auf der Basis von Hauptgruppen‐Elementen

“…[127] Die so erzeugten Polymere mit dreifach-koordiniertem Bor weisen eine Reihe faszinierender Eigenschaften auf, darunter die verstärkte Fluoreszenzlçschung durch Fluorid-Ionen [121, 123b,128] und ein Fluoreszenzansprechvermçgen auf thermische Neutronen (Szintillation). [133] Diese Polyferrocene sind redoxaktiv und neigen dazu, bei (teilweiser) Oxidation der Fe-Zentren halbleitend zu werden. Der Einbau von Pn III -Zentren zwischen Vinylen-, Alkinylen-oder Arylenbausteinen führt zu Polymeren, die nicht nur eine Verlängerung der Konjugation durch s-p-Konjugation aufweisen, sondern auch potenziell auf Lewis-Säure-Bindung oder Oxidation zur formalen Pn V -Oxidationsstufe reagieren.…”