Organoiron monomers

Reaction of complex 31 with 5-norbomene-2-carboxylic acid (16) yielded the organoiron monomer 32. ROMP of monomer 32 using Grubbs catalyst (18) gave... 

Polymers 39 containing both neutral and cationic organoiron moieties as well as azo dyes in their backbone were isolated from the condensation polymerization of azo dye-containing organoiron monomers 37 with various N-, S-, and 0-containing... 

There have also been many studies of the polymerization kinetics of organoiron monomers these have shown that such polymerizations often do not follow the same rate laws as organic monomers. Ferrocene-substituted polymethacrylates possessing nonlinear optical (NLO) properties were reported by Wright and coworkers." The copolymerization of the ferrocenyl-fimctionalized monomer (5mol%) 14 with methyl methacrylate 15 yielded the organometaUic polymer 16, as shown in scheme 4." This polymer displayed second-harmonic-generation activity and possessed... 

Organoiron polynorbomenes containing azo dyes have been synthesized through ROP of azo dye functionalized organoiron monomers (scheme 21). Polymers 73a and 73b displayed molecular weights of approximately 31,600, and cyclic voltammetry showed reversible reductions of the iron centers between -1.2 to -1.4... 

Scheme 8 shows the synthesis of polyacrylate 86 containing pendent ferrocenyl groups via the radical-initiated polymerization of the organoiron monomer 85. ... 

Polymerization of organoiron monomers has also resulted in the production of liquid crystalline polymers containing ferrocene units in their sidechains. " Scheme 6 illustrates Deschenaux s free-radical synthesis of ferrocene functionalized thermotropic liquid crystalline polymethacrylates Monomer 31 and its corresponding polymer 32 exhibited enantiotropic smectic A and C phases. 

Polymethacrylates and polystyrenes with cationic cyclopentadienyliron moieties coordinated to their sidechains were prepared by radical polymerization of their corresponding organoiron monomers as shown in Scheme 19. Electrochemical analysis showed that the cyclopentadienyliron coordinated monomers (74) and polymers (75) underwent reversible reduction processes. Photolytic demetallation of die cyclopentadienyliron-coordinated polymethacrylates resrrlted in the corresponding organic analogs with M =48,000-68,000. 

The synthesis of cationic organoiron containing polymethacrylates and polystyrenes has been reported. The radical polymerization of methacrylate and styrene monomers containing cationic cyclopentadienyliron complexes produced polymers with cationic cyclopentadienyliron complexes in their side chains (Scheme 2.57).265,266 Monomer 216 and polymer 217 were both redox active and underwent reversible reduction processes. An organic analog of the cationic organoiron polymer was obtained by photolytic cleavage of the cationic cyclopentadienyliron... 

Recently, we reported the synthesis of azo dye-functionalized organoiron complexes from the reaction of the bimetallic organoiron complex 3 with azo dyes 4 (Scheme 7.2). These monomers displayed excellent solubility in polar organic solvents and were isolated as vibrantly colored powders ranging from orange to purple in good yields. 

A second method for the synthesis of organometallic polynorbomenes containing a bound azo dye involved the reaction of T -chlorotoluene- n -cyclopentadienyliion complex 21 with bifunctional azo dyes to yield the azo dye-containing organoiron compounds, which wctc then further reacted with 5-norbomene-2-carboxylic acid (16) to form the azo dye functionalized norbomene monomers, 24, shown in Scheme 7.7. 

Polymers containing both netural and cationic iron moieties have been prepared from organoiron complexes containing ferrocene and azo dyes in the main chain with pendent cationic iron units. The monomers were prepared by first reacting bifunctional azo dyes 34 with the organoiron complex (1) (Scheme 7.11). 

The azo dye-functionalized organoiron complexes 35 were isolated in good yields and contained a hydroxyl group available for condenstation with l.l -fer-rocene dicarbonyl chloride (36) (Scheme 7.12). The monomers 37 were isolated as vibrantly colored materials in high yields that showed good solubility in polar organic solvents. 

The synthesis of polyaromatic ethers (37) and thioethers containing azobenzene dyes in their sidechains has been achieved. These polymers were prepared by reaction of cyclopentadienyliron-complexed azobenzene monomers with various dinucleophiles. These organoiron polymers were bright orange or red, and could be bleached by irradiating the polymer in a solution containing hydrogen peroxide. 

Monomers 49 and 50 were subsequently reacted with 2d, 7, and lOd in the presence of potassium carbonate in DMF, resulting in the formation of polymers 51a-f as shown in Scheme 14. These polymers are unique in that they bear neutral ferrocenyl units in their backbones and cationic cyclopentadienyliron moieties pendent to their backbones. These polymers were isolated as orange solids in yields ranging from 86 to 91%. These organoiron polymers demonstrated good solubility in polar organic solvents such as DMF and DMSO. 

It was also of interest to examine the polymerization of monomer 11 via nucleophilic displacement of the chloro groups with oxygen- and sulfiu-based nucleophiles. Our previous studies have shown that fliese reactions proceed under nuld reaction conditions to yield soluble polycationic organoiron polymers. " Scheme 5 shows the reaction of 11 with 14a and 14b to produce polymers 15a and 15b. 

We have reported that norbornene monomers functionalized with arene complexes also undergo ring-opening metathesis polymerization to produce the corresponding cyclopentadienyliron-coordinated polynorbomenes. Scheme 13 shows the synthesis of polymers containing aromatic ether sidechains functionalized with organoiron moieties. ... 

The reaction of olefinic monomers with organoiron complexes has allowed the synthesis of mainchain ferrocene-containing polymers. This new class of organometalhc polymers was formed through the reaction of various diolefins with l,r-dimercaptoferrocene 19 or l,r-bis(2-mercaptoethyl)ferrocene. The reaction of l,r-dimercaptoferrocene with 1,4-butandiol dimethacrylate (scheme 6) produced polymer 21 via base-catalyzed polyaddition. 

Ring-opening metathesis polymerization (ROMP) of norbornene monomers (91) (Scheme 11) fimctionalized with cyclopentadienyliron cations has been accomplished using transition metal catalysts to yield the corresponding organoiron polymer (92). The resulting polynorbomene has the metallic moieties present in the... 

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