Properties of Dioxybiphenyl- and Chiral Dioxybinaphthylphosphazene Copolymers with Propyl−Carboxylate−Phenoxy Units and the Randomization of the Substitution Reactions of Poly(dichlorophosphazene)

Abstract

The reaction of [NPCl2] n first with 2,2'-dihydroxybiphenyl and K2CO3 or (R)-(+)-2,2'-dihydroxy-1,1'-binaphthyl and Cs2CO3, and subsequently with HO−C6H4−CO2Prn and Cs2CO3, gave the phosphazene copolymers {[NP(O2C12H8)]1 - x [NP(O−C6H4−CO2Prn)2] x } n [x = 0.2 (1a), 0.35 (1b), 0.5 (1c), 0.7 (1d), and 0.85 (1e)] and the chiral analogues {[NP(O2C20H12)]1 - x [NP(O−C6H4−CO2Prn)2] x } n [x = 0.2 (2a), 0.4 (2b), 0.45 (2c), 0.5 (2d), 0.55 (2e), 0.7 (2f), and 0.8(2g)]. The study of their properties as a function of the composition have revealed systematic changes in the electronic structure of the macromolecules, in the interplanar distances of their mesophases and in glass transition temperatures. The latter variation has demonstrated the strictly alternating nature of the copolymeric structures in the series 1 and 2. This is an experimental evidence supporting that the substitution of Cl in the [NPCl2] n with the bifunctional reagents or 2,2'-dihydroxybiphenyl and (R)-(+)-2,2'-dihydroxy-1,1'-binaphthyl as promoted by alkali carbonates are essentially random for all values of x and that the chirality of the binaphthyls has no stereochemical effect.

Covalently Bonded Bis(phosphane)gold(I) Cations in a Cross‐Linked Phosphazene Polymeric Matrix as Recyclable Supported Catalysts for Thermal and Microwave‐Assisted Hydration of Alkynes

“…The severe steric hindrance in the region of the active centres explains why less donor and bulky alkynes are not activated by this catalyst. Moreover, as we have previously demonstrated both experimentally and theoretically, [13] the acid present in the reaction media is capable of protonating the phosphazene N atoms opening the P=N bonds of the chains to the water molecules inducing their slow hydrolysis. The subsequent chain degradation would have a destabilising effect on the solid matrix structure causing its fragmentation affecting the physical state and making the recovery more demanding.…”

“…[9a,11] Recently, [12] we reported the synthesis of cross-linked polymeric materials of composition { (Figure 1), which makes them comparable to hybrid inorganic-organic frameworks, is based on the apparently regular distribution of the two phosphazenic units present in the chains as demonstrated for similar co-polyphosphazenes. [13] Although, the parent discrete bis(phosphane) complex [Au(PPh 3 ) 2 ]PF 6 has been described as a noncatalyst for the hydration of alkynes, [1e] we have found that this complex is, in fact, very efficient for terminal alkynes in the presence of sulfuric acid, particularly if microwave radiation is used to increase the reaction temperature. We also observed that the new related gold …”

Solid State Morphology and Size Tuning of Nanostructured Platinum Using Macromolecular Complexes

“…Chitosan induces the formation of smaller nanoparticles (6 nm) for the 1:1 molar ratio than for 1:5 ratios. Unlike to the previously reported other solid state method [53][54][55][56][57][58][59][60] which start from precursor contained phosphazene derivatives linked to metal and organometallic fragments the here reported method allow the formation of phase pure metal oxides.…”

Designed synthesis of metal-organic frameworks containing gold(I) cations supported in phosphazene-phosphine polymeric matrices

“…Calc. for C 18 H 13 (4) To a solution of AuCl(THT) (0.039 g, 0.121 mmol) in THF (50 mL), solid 3a (0.5 g, 1.61 mmol, 0.24 mmol of free PPh 2 ) and the mixture was stirred at room temperature for 2. The 1 H NMR spectrum of the liquid showed only the presence of un-coordinated THT.…”