Giant Organometallic Networks Derived from Ferrocenepolysulfides

Galloway, Collin P.; Rauchfuss, Thomas B.

doi:10.1002/anie.199313191

Cited by 58 publications

(21 citation statements)

References 17 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…In early 1992, a novel atom-abstraction-induced ROP process was described [60]. The molecular weights have been determined to be in the range M w = 12,000±359,000 for 3.64 (R = n-Bu, R' = H) and 25,000 in the case of a less soluble copolymer formed from monomers 3.63 with (R = R' = H) : (R = n Bu, R' = H) in a ratio of 53 : 47 [173,175]. 3.23).…”

Section: Polyferrocenylphosphine Block Copolymersmentioning

confidence: 99%

Main‐Chain Polymetallocenes with Short Spacer Groups

Manners

2003

Synthetic Metal‐Containing Polymers

View full text Add to dashboard Cite

Although the first polymers with metals in the side chains were prepared as early as the mid-1950s, the development of main-chain metal-containing polymers has been much slower. This is particularly the case when the metal atoms are linked together by short spacers and their close spatial proximity might be expected to give rise to interesting properties due to the presence of metal-metal interactions. This chapter focuses on materials of this type which contain metallocene units in the main chain, as polymers possessing these organometallic moieties dominate this particular area. Analogous materials with longer spacers, defined as those having more than three atoms between the p-coordinated metal centers, are structurally much more diverse but, in general, less well-studied. These polymers will be discussed in Chapter 4.As in the case of side-chain metal-containing polymers (Chapter 2), the development of main-chain polymers that incorporate metallocene units has represented a major area of research. Since the discovery and structural elucidation of ferrocene, the prototypical metallocene, a vast organic chemistry has been demonstrated for this species, and the reversible one-electron oxidation to the blue ferrocenium ion has been much exploited [1±3]. The exciting possibilities for polyferrocenes with short spacers between the metal-containing units are illustrated by the results of detailed studies of dimeric species. Thus, oxidation of biferrocenes and biferrocenylenes has provided access to mixed-valent species such as 3.1 and 3.2, respectively, in which the unpaired electrons are delocalized on a variety of time scales depending on substituent, counterion, and solid-state environmental effects [4,5]. Many of the other properties of molecular ferrocenes also make their incorporation into polymer structures highly desirable. For example, liquid-crystalline ferrocenes have been prepared and ferrocene-based charge-transfer materials such as 3.3 have attracted considerable attention with respect to their cooperative magnetic properties [6, 7]. Equally encouraging are the facts that ferrocene is easy to prepare, cheap and commercially available, and air-, moisture-, and thermally-stable.As described in Chapter 2, attempts to incorporate ferrocene into the side-chain structure of polymers have been very successful. In this case, a variety of high

show abstract

Section: Polyferrocenylphosphine Block Copolymersmentioning

confidence: 99%

Main‐Chain Polymetallocenes with Short Spacer Groups

Manners

2003

Synthetic Metal‐Containing Polymers

View full text Add to dashboard Cite

show abstract

“…[163][164][165][166] If the polymerization reactions were conducted in THF or DMF, insoluble polymers were isolated, however soluble high-molecular-weight polymers could be prepared by using a mixed solvent system consisting of dichloromethane and THF. [164] UV irradiation of the polymers in air resulted in polymer degradation, however, in the absence of air, the polymers were stable.…”

Section: Ring-opening Polymerizationmentioning

confidence: 99%

“…Three-dimensional networks were also prepared by the desulfurization of [Fe(C 5 H 3 ) 2 (S 3 ) 2 ]. [166] These polymers could be made soluble by incorporating butyl groups on the cyclopentadienyl rings.…”

Section: Ring-opening Polymerizationmentioning

confidence: 99%

Organometallic Polymers of the Transition Metals

Abd‐El‐Aziz

2002

Macromol. Rapid Commun.

165

View full text Add to dashboard Cite

This article provides a comprehensive review of the synthesis, properties and applications of organometallic polymers of the transition metals. The different classes of organometallic polymers are described according to their structural make‐up, as well as by their methods of synthesis. A number of examples of each class are given to emphasize the richness and diversity in these areas of research. In addition to linear polymers, hyperbranched, crosslinked, star and dendritic polymers are also described. The properties that transition metal‐containing organometallic polymers possess, as well as the applications that these materials have found in various domains are highlighted. magnified image

show abstract

“…Poly(ferrocenylene persulfides) possess a range of novel properties (173)(174)(175). They are photosensitive and the S S bonds can be reversibly reductively cleaved with Li[B(C 2 H 5 ) 3 H] and then regenerated upon oxidation with I 2 .…”

Section: Other Polyferrocenesmentioning

confidence: 99%

“…Their electrochemical behavior is similar to that detected for polyferrocenylsilanes except that the interaction between the iron sites appears to be even greater. The atom abstraction route using P( t C 4 H 9 ) 3 as a desulfurization agent has also been extended to the preparation of other poly(ferrocenylene persulfides) with t-butyl substituents and also high molecular weight (M w = 50,000-1,000,000) network polymers by the use of [3]ferrocenophanes with two trisulfido bridges as monomers (174).…”

Section: Other Polyferrocenesmentioning

confidence: 99%

Inorganic Polymers

Bourke¹,

Manners²

2001

Encyclopedia of Polymer Science and Technology

View full text Add to dashboard Cite

The thermal ROP route requires the synthesis and careful purification of the cyclic trimer [Cl 2 PN] 3 and the use of elevated temperatures where control of molecular weight is very difficult and cross-linking can take place at high conversion, which can limit the yield. INORGANIC POLYMERSVol. 3to phosphazene polymers, which may well facilitate more rapid and extensive commercialization.Monomer Synthesis. Both the ROP and condensation routes to poly(dichlorophosphazene) require high purity monomers. For the traditional ROP process, ultrahigh purity [NPCl 2 ] 3 is required. The most common method for its preparation is through the reaction of PCl 5 with NH 4 Cl in a high boiling halogenated solvent, such as chlorobenzene or tetrachloroethane, at 150 • C. The yields can approach 70-80% under specialized conditions, but 50% is more typical (25). The phosphoranimine most commonly used in the aforementioned condensation route to poly(dichlorophosphazene) is Cl 3 P NSi(CH 3 ) 3 . The synthesis of this compound has been described (21) and is based on a modification of an earlier procedure (26) involving the reaction of PCl 5 with LiN(Si(CH 3 ) 3 ) 2 at −78 • C in hexane. However, the purification required by this method is a challenge and leads to an overall yield of <40%.It has also been reported that the reaction of N(Si(CH 3 ) 3 ) 3 with PCl 5 can be manipulated to maximize yields of either the cyclic trimer (76%) or the pure phosphoranimine monomer (40%) through variations in reaction conditions (25). These reactions use milder conditions than previously reported methods, with higher yields. In addition, the major side product, (CH 3 ) 3 SiCl, can be recycled to form one of the starting materials, N(Si(CH 3 ) 3 ) 3 .N-Silylphosphoranimines with alkyl and aryl substituents can be synthesized by reaction of commercial starting materials such as PCl 3 , ((CH 3 ) 3 Si) 2 NH, and Grignard reagents by way of a three-step process, with typical yields of 60-70%. These precursors are also accessible via a "one-pot" synthesis, which requires only isolation of the final product with yields of about 75% (3).Uses. Some of the most useful polyphosphazene derivatives are fluoroalkoxy derivatives, and amorphous copolymers are very useful as flame-retardant, hydrocarbon-solvent, and oil-resistant elastomers and have found aerospace and automotive applications. Polymers such as the amorphous comb polymer poly[bis(methoxyethoxyethoxy)phosphazene] (8) are of considerable interest as components of polymeric electrolytes in battery technology (1). Vol. 3 INORGANIC POLYMERS 35Polyphosphazenes are also of interest as biomedical materials and bioinert, bioactive, membrane-forming, and bioerodable materials (1).

show abstract

Giant Organometallic Networks Derived from Ferrocenepolysulfides

Cited by 58 publications

References 17 publications

Main‐Chain Polymetallocenes with Short Spacer Groups

Main‐Chain Polymetallocenes with Short Spacer Groups

Organometallic Polymers of the Transition Metals

Inorganic Polymers

Contact Info

Product

Resources

About