The B all and N all: Soluble, linear, high molecular weight polyaminoborane homopolymers copolymers have been synthesized by iridium-catalyzed dehydrocoupling of readily available amine–borane adducts RNH2⋅BH3 (R=H, Me, nBu). Supporting information for this article is on the WWW under http://www.wiley-vch.de/contents/jc_2002/2008/z801197_s.pdf or from author. Please note: publisher not responsible content functionality any supporting supplied authors. Any queries (other than missing content)...

Getting in shape: Stable pointed-oval-shaped micelles of uniform size and shape (see TEM image) were prepared by extending the crystallization-driven living self-assembly method to crystalline core-forming polyferrocenylsilane diblock copolymers with corona-forming coblocks poly(2-vinylpyridine) polyphosphazene. The subsequently used as precursors hierarchical micelle architectures. Detailed facts importance specialist readers are published "Supporting Information". Such documents...

B und N als Rückgrat: Lösliche lineare Polyaminoboran-Homopolymere -Copolymere mit hohen Molekulargewichten wurden durch die iridiumkatalysierte Dehydrokupplung der leicht erhältlichen Amin-Boran-Addukte RNH2⋅BH3 synthetisiert (R=H, Me, nBu).

Abstract We herein report the formation of two complex nanostructures, toroidal micelles and bicontinuous nanospheres, by self‐assembly single structurally simple crystalline‐ b ‐coil diblock copolymer poly[bis(trifluoroethoxy)phosphazene]‐ ‐poly(styrene), PTFEP‐ ‐PS, in one solvent (THF) without additives. The nature these nanostructures solution was confirmed DLS cryo‐TEM experiments. morphologies are related means a new type reversible morphological evolution, bicontinuous‐to‐toroidal,...

A new environmentally-friendly and air-tolerant protocol for the Cu-MOF catalysed ATRP of MMA in a biorenewable deep eutectic solvent is reported, with both catalyst being recycled up to six consecutive times.

Despite their ubiquitous presence in synthesis, the use of polar organolithium reagents under environmentally benign conditions constitutes one greatest challenges sustainable chemistry. Their high reactivity imposes severely restrictive protocols (e.g., moisture- and oxygen-free, toxic organic solvents, inert atmospheres, low temperatures, etc.). Making inroads towards meeting this challenge, a new air- moisture-compatible organolithium-mediated methodology for anionic polymerization...

A scalable CuI-catalyzed Goldberg C–N coupling between aryl iodides and amides is reported either in DESs or water.

Abstract Challenging conventional wisdom that s‐block organometallic reagents such as Grignard or organolithiums need to be used under protecting inert atmosphere (N 2 Ar), employing dry organic solvents with a strict temperature control, this Minireview focusses on recent advances the use of these commodity while operating air, at room and in presence moisture. Key for success approaches has been following sustainable solvents: i ) water; ii Deep Eutectic Solvents (DESs ); iii...

A modular, three-component, and sustainable one-pot/one-step protocol has been developed for the efficient regioselective synthesis of libraries γ-keto sulfones phosphine oxides through concurrent C-C C-X bond formation (X = S or P). The acidic eutectic mixture ChCl/p-TSA·H2O (1:2) (ChCl choline chloride; p-TSA p-toluenesulfonic acid) serves as both promoter reaction medium. This transformation involves a cascade process comprising three consecutive steps: i) hydration terminal alkynes to...

In this study, we demonstrate that varying the initial concentration of poly-[bis(trifluoroethoxy)phosphazene]-b-poly(styrene) (PTFEP55-b-PS50) block copolymer enables formation diverse, well-defined nanomorphologies through self-assembly in tetrahydrofuran (THF). By adjusting concentration, spherical micelles (0.1 mg/mL), bicontinuous (0.33 toroidal (2.0 cylindrical (10 and vesicles (50 mg/mL) were successfully prepared. This simple methodology, using a single solvent no additives, allowed...

In this study, we demonstrate that varying the initial concentration of poly‐[bis(trifluoroethoxy)phosphazene]‐bpoly(styrene) (PTFEP55‐b‐PS50) block copolymer enables formation diverse, well‐defined nanomorphologies through selfassembly in tetrahydrofuran. By adjusting concentration, spherical micelles (0.1 mg/mL), bicontinuous (0.33 toroidal (2.0 cylindrical (10 and vesicles (50 mg/mL) were successfully prepared. This methodology, using a single solvent no additives, allowed for...

A simple and convenient one-pot synthesis of THF solutions high molecular weight poly(dichlorophosphazene) [NPCl(2)](n), or the (15)N isotopomer [(15)NPCl(2)](n), starting directly from PCl(5) NH(4)Cl (15)NH(4)Cl in a solution 1,2,4-trichlorobenzene presence sulfamic acid calcium sulfate dihydrate, is described. The [NPCl(2)](n) THF, which are obtained free poly(tetrahydrofuran) by preparing them K(2)CO(3), can be reacted with phenols, biphenols, even HO-CH(2)CF(3) K(2)CO(3) Cs(2)CO(3) to...

Highly polarized lithium phosphides (LiPR2 ) were synthesized, for the first time, in deep eutectic solvents as sustainable reaction media, at room temperature and absence of protecting atmosphere, through direct deprotonation both aliphatic aromatic secondary phosphines (HPR2 by n-BuLi. The subsequent addition in-situ generated LiPR2 to aldehydes or epoxides proceeded quickly chemoselectively, thereby allowing straightforward access corresponding α- β-hydroxy phosphine oxides, respectively,...

ADVERTISEMENT RETURN TO ISSUEPREVCommunication to the...Communication the EditorNEXTPoly(ferrocenylsilane-b-polyphosphazene) (PFS-b-PP): A New Class of Organometallic−Inorganic Block CopolymersAlejandro Presa Soto and Ian Manners*View Author Information School Chemistry, University Bristol, BS8 1TS, U.K.* Corresponding author. E-mail: [email protected]Cite this: Macromolecules 2009, 42, 1, 40–42Publication Date (Web):December 4, 2008Publication History Received23 July 2008Revised27 October...

The counteranion associated with the cationic initiator [Cl3P═N═PCl3]+ ([4]+) generated during PCl5-initiated living, chain growth polycondensation of N-silylphosphoranimine Cl3P═NSiMe3 (3) to give poly(dichlorophosphazene), [N═PCl2]n (2), has been found have a dramatic effect on polymerization. When [4]+ was changed from PCl6– or Cl– weakly coordinating anions [BAr*F4]− and [BArF4]− (Ar*F = 3,5-{CF3}2C6H3, ArF C6F5) instead polymerization 3 being complete in 4–6 h, no reaction observed...

The sequential living polymerization of N-silylphosphoranimines for the synthesis polyphosphazene-b-polyphosphazene diblock copolymers (PP-b-PP) has been studied both experimentally and theoretically. For experiments, BrMe2P═N–SiMe3, [Cl3P═N═PCl3][X] (X = PCl6–, Cl–), Cl3P═N–SiMe3, ClMe2P═N–SiMe3, [Me3P═N═PMe2Cl]+ were used as representative model reagents. Density functional theory (DFT) calculations in gas phase adjusted solvent effects on [Cl3P═N═PCl3]+, ClMe2P═N–SiMe3 confirmed...

The room temperature addition of stoichiometric amounts trimethyl phosphite, P(OMe)3, to N-silyl(halogeno)organophosphoranimines BrRR′P═NSiMe3 in chlorinated solvents led the direct formation high molecular weight polyphosphazenes [RR′P═N]n. majority polymerizations were complete within 18 h. polymers prepared include poly(dialkylphosphazenes) (e.g., [nBu2P═N]n 1b), poly(alkylarylphosphazenes) [PhMeP═N]n 1d), new materials featuring unsaturated substituents [nHex{H2C═C(H)CH2}P═N]n 1n), and...

Abstract The unexpected finding that the complex [Au(PPh 3 ) 2 ]PF 6 ( C1 catalyses specific hydration of 1‐octyne, p ‐phenoxyphenyl)acetylene, phenylacetylene, ‐chlorophenyl)acetylene and benzylacetylene at 100 °C in presence H SO 4 THF or methanol as solvents, specially using microwave radiation, led to first gold(I) recyclable catalysts for this reaction. phosphazene polymeric framework idealised formula {[NP(O C 12 8 )] 0.85 [NP(OC PPh (AuPF 0.5 ] 0.15 } n C2 ), newly synthesised...

This Perspective discusses the development of new routes to polyphosphazenes, [R(2)P[double bond, length as m-dash]N](n), that occur at ambient temperature and, in some cases, allow molecular weight control and access narrow distributions block copolymers. For example, room silyl-carborane initiated ring-opening polymerisation (NPCl(2))(3) is described together with chain growth condensation polymerisations phosphoranimines Cl(3)P[double m-dash]NSiMe(3) BrMePhP[double m-dash]NSiMe(3). Recent...

Abstract A series of optically active helical polyphosphazene block copolymers general formula R [NP(O 2 C 20 H 12 )] n ‐ b ‐[NPMePh] m ( 7 a – c ) was synthesized and characterized. The polymers were prepared by sequential living cationic polycondensation N ‐silylphosphoranimines using the mono‐end‐capped initiator [Ph 3 PNPCl ][PCl 6 ] 5 exhibit low polydispersity index (ca. 1.3). temperature dependence specific optical activity ([ α D , relative to that for homopolymers ‐[NP(O 8 / S...

Organocatalysis and highly-polar s-block organometallic chemistry (RLi) work together in water, under air at room temperature for the selective ultrafast synthesis of tertiary alcohols.

The highly efficient biodeoximation of aromatic ketoximes, promoted by the enzymatic oxidative system laccase/TEMPO/O2, has been successfully assembled with fast and chemoselective addition highly-polar s-block organometallic reagents (RLi/RMgX) en route to highly-substituted tertiary alcohols. By using this hybrid one-pot tandem protocol, alcohols have selectively synthesized in good yields under mild bench-type reaction conditions (room temperature, absence a protecting atmosphere aqueous...

Abstract The polyphosphazene random copolymer containing diphenylphosphane ligands {[NP(OC 6 H 4 PPh 2 ) ] 0.4 [NP(O C 12 8 )] 0.6 } n ( 1a (O = 2,2′‐dioxy‐1,1′‐biphenyl), and the chiral binaphthoxy analogues 0.1 20 0.9 [O R )‐2,2′‐dioxy‐1,1′‐binaphthyl] 1b 0.2 10 Br 0.8 )‐2,2′‐dioxy‐6,6′‐dibromo‐1,1′‐binaphthyl] 1c ), reacted in dichloromethane at room temperature with appropriate amounts of dimeric complex [Ru(η ‐ p ‐cymene)Cl(μ‐Cl)] to give corresponding polymeric (phosphane)Ru II...

Wie ein Ei dem andern: Die Herstellung von stabilen spindelförmigen Micellen einheitlicher Größe und Form (siehe TEM-Bild) gelingt durch Anwendung der kristallisationsgetriebenen lebenden Selbstorganisation auf kristalline kernbildende Polyferrocenylsilan-Diblockcopolymere mit coronabildenden Coblöcken aus Poly(2-vinylpyridin) Polyphosphazen. dienten anschließend als Vorstufen zum Aufbau hierarchischen Micellarchitekturen.

The preparation of long-term-stable giant unilamellar vesicles (GUVs, diameter ≥ 1000 nm) and large (diameter 500 by self-assembly in THF the crystalline-b-coil polyphosphazene block copolymers [N=P(OCH2CF3)2 ]n-b-[N=PMePh]m (4 a: n=30, m=20; 4 b: n=90, c: n=200, m=85), which combine crystalline [N=P(OCH2CF3)2] amorphous [N=PMePh] blocks, both are flexible, is reported. SEM, TEM, wide-angle X-ray scattering experiments demonstrated that stability these GUVs induced crystallization blocks at...