New Organofunctional Cyclophosphazene Derivatives

Allen, Christopher C. R.; Hayes, Robert A.; Myer, Charles N.; Freund, Amy; Kearney, Marie E.

doi:10.1080/10426509608046203

Cited by 3 publications

(5 citation statements)

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“…An additional source shortfall of current is due to precipitation of the oxidized compound on the electrode surface, which would in effect decrease the electrode surface area and thus the current. In an attempt to overcome this problem, voltammograms of 5 and 7 were obtained using a different supporting electrolyte, tetrakis(perfluorophenyl) borate, which has been shown to increase the solubility of oxidized analytes and prevent electrode precipitation . Some improvement in the normal pulse voltammograms was observed, but the upward turn at the end of the normal pulse voltammogram of 7 remained indicating some precipitations still occurred.…”

Section: Resultsmentioning

confidence: 99%

N-(Ferrocenylmethyl)-N-methylaminocyclotriphosphazenes

Myer

Allen

2001

Inorg. Chem.

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The reactions of N-(ferrocenylmethyl)-N-methylamine, C(5)H(5)FeC(5)H(4)CH(2)(Me)NH, with hexachlorocyclotriphosphazene, N(3)P(3)Cl(6), led to the formation of the N-(ferrocenylmethyl)-N-methylaminocyclotriphosphazene derivatives, N(3)(-)P(3)Cl(6-n)[N(Me)CH(2)C(5)H(4)FeC(5)H(5)](n) (n = 1-3). Only small amounts of higher degrees of substitution could be detected. In the case of the disubstituted products, the ratio of isomers was dependent on the polarity of the solvent. In nonpolar solvents the ratio was trans > geminal > cis while in acetonitrile only equal amounts of trans and cis isomers were observed. The reaction of N-(ferrocenylmethyl)-N-methylamine with (methacryloylbutenedioxy)pentachlorocyclotriphosphazene, N(3)P(3)Cl(5)O(CH(2))(4)OC(O)C(Me)=CH(2), gives the surprising geminal isomer 2,2-N(3)P(3)Cl(4)[O(CH(2))(4)OC(O)C(Me)=CH(2)]N(Me)CH(2)C(5)H(4)FeC(5)H(5) and the tris derivative 2,2',4-N(3)P(3)Cl(3)[O(CH(2))(4)OC(O)C(Me)=CH(2)][N(Me)CH(2)C(5)H(4)FeC(5)H(5)](2). All of the phosphazene derivatives were characterized by elemental analyses, mass spectrometry, IR and NMR ((1)H, (13)C, (31)P) spectroscopy, and electrochemical techniques (cyclic, normal pulse, and differential pulse voltametry). The compounds all undergo a single, reversible oxidation reduction process.

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Section: Resultsmentioning

confidence: 99%

N-(Ferrocenylmethyl)-N-methylaminocyclotriphosphazenes

Myer

Allen

2001

Inorg. Chem.

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“…In response to these observations, emphasis has been shifted to cyclophosphazene monomers in which an insulating group is interposed between the olefinic center and the cyclophosphazene. Using this strategy, our group − ,− as well as those of Inoue , and van de Grampel , have produced a wide range of polymers and copolymers with cyclotriphosphazenes as substituents. These insulating moieties are complex functional groups such as aryl, , aryloxy, , or polyalkyloxy 10,11 units.…”

Section: Introductionmentioning

confidence: 99%

“…Using this strategy, our group [1][2][3][4][5][6][9][10][11][12] as well as those of Inoue 1,13 and van de Grampel 1,14 have produced a wide range of polymers and copolymers with cyclotriphosphazenes as substituents. These insulating moieties are complex functional groups such as aryl, 9,14 aryloxy, 12,13 or polyalkyloxy 10,11 units. In each case, the complexity of the organic moiety obscures any direct relationships between the insulating unit and the reactivity of the olefin or the physiochemical behavior of the resulting polymers.…”

Section: Introductionmentioning

confidence: 99%

Poly[(vinyloxy)cyclophosphazenes]

et al. 2001

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The vinyloxycyclophosphazene derivatives, N3P3Cl5OCHCH2 (1) and N4P4Cl7OCHCH2 (6), undergo radical polymerization to produce the highly functionalized homopolymers [CH(ON3P3Cl5)CH2] n (7) and [CH(ON4P4Cl7)CH2] n (8). These materials undergo a remarkable two-step thermal decomposition process. The first step is an exothermic cross-linking reaction involving the elimination of HCl at modest temperatures. The activation energy for the first step is lower for 7 than for 8. The second step is an endothermic elimination of the oxo-bridged cyclophosphazene dimer, (N3P3Cl5)2O. Copolymers have been obtained from mixtures of 1 and 6. The calculated reactivity ratios show a preference for incorporation of 1 over 6 into the copolymers. Attempted copolymerization of 1 with styrene leads to mixtures of the respective homopolymers. Attempts to polymerize N3P3X5OCHCH2 [(X = F(2), OCH3 (3), OCH2CF3 (4), N(CH3)2 (5)] lead to various outcomes including insoluble materials, oligomers, or recovery of unreacted monomer. The sensitivity of the polymerization to the nature of the phosphazene substituents has been related to monomer electronic structure and reactivity of the exocyclic groups.

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“…In the case of exocyclic groups containing an olefinic moiety, addition polymerization *Correspondence to: Christopher W. Allen reactions lead to organic backbone polymers with the inorganic ring system as a substituent [2,3]. We have recently focused on the synthesis and polymerization of cyclophosphazenes with methacrylates as the exocyclic group [4][5][6]. In the course of these investigations, it was discovered that the most convient of the methacrylate derivatives, the phosphazene derivative obtained from 2-hydroxyethyl methylmethacrylate, N 3 P 3 Cl 5 O(CH 2 ) 2 OC(O)C(CH 3 -‫ס‬CH 2 , undergoes a slow phosphazene-phosphazane rearrangement [5].…”

Section: Introductionmentioning

confidence: 99%

“…The preliminary report of the mechanism of this rearrangement indicated a firstorder process involving dissociation of the carbonoxygen bond linking the organic component to the phosphazene ring [5]. We are exploring routes to methacrylate monomers for which this process is obviated [6]. In this article, we report one such approach involving anchoring the exocyclic group to the phosphazene using two points of attachment, i.e., via spirocyclic derivatives.…”

Section: Introductionmentioning

confidence: 99%