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Ian Manners

Publications and source records attributed to Ian Manners.

At least 19 recordsLinked to original sources
PubMed2006

Transition-metal-catalyzed dehydrocoupling: a convenient route to bonds between main-group elements.

The development of transition-metal-catalyzed dehydrocoupling reactions as a synthetic method for the formation of main-group element-element bonds provides an increasingly attractive and convenient alternative to traditional routes such as salt metathesis/elimination-type reactions. Since the first reported examples in the early 1980s, there has been a rapid expansion of this field, with extensions to a wide variety of metal-mediated homonuclear and heteronuclear bond-forming processes. Applications of this new chemistry in molecular and polymer synthesis, materials science, hydrogen storage and the transfer hydrogenation of organic substrates are attracting growing attention. An overview of this emerging area is presented in this Concepts article with a focus on recent results.

Journal Article↗
PubMed2006

Reactions of P-donor ligands with N-silyl(halogeno)organophosphoranimines: formation of cations with P-P coordination bonds and poly(alkyl/aryl)phosphazenes at ambient temperature.

A series of phosphine donor-stabilized N-silylphosphoranimine salts [R'3P.PR2=NSiMe3]+Br- were prepared from the direct reaction between the phosphoranimines BrR2P=NSiMe3 (R = Me, OCH2CF3) and the tertiary phosphines nBu3P and Me3P. The 1JPP values of these salts exhibit an unusual dependence on the substituents at the phosphoranimine acceptor and appear to reflect an electronic push-pull mechanism. Employment of phosphites as the phosphorus donor results in the generation of high molecular weight poly(alkyl/aryl)phosphazenes at ambient temperature. This preparative route is potentially advantageous over the conventional thermal polycondensation route.

Journal Article↗
PubMed2006

Phosphine-mediated dehalogenation reactions of trichloro(N-silyl)phosphoranimines.

The reaction of N-(trimethylsilyl)phosphoranimine Cl3P=NSiMe3 (1) with nBu3P or Ph3P yields the N-(dichlorophosphino)phosphoranimines nBu3P=NPCl2 (4a) or Ph3P=NPCl2 (4b), respectively. Detailed studies of this reaction indicate a mechanism that involves the reductive dechlorination of 1 by the tertiary phosphine to yield nBu3PCl2 (5a) or Ph3PCl2 (5b) with the apparent formation of the transient chlorophosphinimine ClP=NSiMe3 (6), followed by condensation of 5a or 5b with 1 to form 4a or 4b and Me3SiCl. Convincing evidence for the proposed mechanism was revealed by studies of the analogous reaction between the N-(triphenylsilyl)phosphoranimine Cl3P=NSiPh3 (8) with nBu3P and Ph3P. These reactions quantitatively generated 5a and 5b and also allowed the correspondingly more stable chlorophosphinimine ClP=NSiPh3 (10) to be identified.

Journal Article↗
PubMed2006

Homogeneous, titanocene-catalyzed dehydrocoupling of amine-borane adducts.

Transition metal catalysis represents a relatively unexplored but potentially useful route to form bonds between main group elements. Previous work in the area of amine-borane adduct dehydrocoupling has exclusively employed late transition metal (e.g., Rh) catalysts which were found to predominantly operate via a heterogeneous mechanism. Herein, we present a new, early transition-metal-catalyzed, homogeneous system which exhibits higher activity.

Journal Article↗
PubMed2006

Carbon nanotubes with small and tunable diameters from poly(ferrocenylsilane)-block-polysiloxane diblock copolymers.

Iron-containing nanostructures produced from various self-assembled poly(ferrocenylsilane)-block-polysiloxane thin films are catalytically active for the initiation and growth of high density, small diameter carbon nanotubes (CNTs). Moreover, the tube diameter and density can be tuned by adjusting the chain lengths of the block copolymer. Iron-containing nanostructures from poly(ferrocenylmethylethylsilane)-b-poly(methylvinylsiloxane) polymer with 25 repeat units of an iron-containing segment and 265 repeat units of a non-iron-containing segment are able to produce CNTs with diameters around or less than 1 nm. Lithographically selective growth of CNTs across a large surface area has been demonstrated using this polymer system. Under the same growth condition, it has been found that the yield of defect-free CNTs varies with the size of the catalytically active nanostructures, which are dictated by the chain lengths of the two blocks. This result indicates that, for a specific-sized catalyst nanocluster, a unique set of growth conditions is required for synthesizing high yield, defect-free CNTs. This finding further addresses the importance of using uniform-sized catalyst-containing nanostructures for consistently achieving high-yield and high-quality CNTs with a minimum number of defects and amount of amorphous carbon.

Journal Article↗
PubMed2006

Photocontrolled living polymerizations.

Living polymerizations involve the creation of polymer chains without significant irreversible chain transfer or chain termination. Such processes are widely used to access well-defined macromolecular materials with controlled architectures, such as block and star polymers. Although this concept was first realized for anionic polymerizations in the 1950s, many key recent advances have been made, most notably in the area of radical polymerization. Here, we report a living photopolymerization that involves photoexcited monomers. Exposure of metal-containing ferrocenophane monomers to Pyrex-filtered light from a mercury lamp (lambda>310 nm) or to bright sunlight in the presence of an anionic initiator leads to living polymerizations, in which the conversion and molecular weight of the resulting polymer can be controlled by the irradiation time. Photoirradiation selectively weakens the iron-cyclopentadienyl bond in the monomer, allowing the use of moderately basic and highly functional-group-tolerant initiators. The polymerization proceeds through attack of the initiator and propagating anion on the iron atom of the photoexcited monomer and, remarkably, the polymerization rate decreases with increasing temperature. Block copolymer formation is possible when the light source is alternately switched on and off in between sequential addition of different monomers, providing unprecedented, photocontrolled access to new types of functional polymers.

Journal Article↗
PubMed2006

Synthesis of ansa-[n]silacyclopentadienyl-cycloheptatrienyl-chromium complexes (n = 1, 2): novel precursors for polymers bearing chromium in the backbone.

Reaction of [(eta5-C5H4Li)(eta7-C7H6Li)Cr]tmeda with a variety of dialkyl(dichloro)silanes in aliphatic solvents afforded the corresponding [1]silatrochrocenophanes. Structural characterization by X-ray diffraction analysis of the [1]silatrochrocenophanes bearing Me2Si, (iPr)2Si, and silacyclobutane bridges revealed tilt angles alpha of 15.56(12) degrees , 15.8(1) degrees , and 16.33(17) degrees , respectively. Analogously, a [2]silatrochrocenophane (6) was prepared in excellent yield by reaction of [(eta5-C5H4Li)(eta7-C7H6Li)Cr]tmeda with 1,2-dichloro-1,1,2,2-tetramethyldisilane. This complex also was characterized structurally and exhibited a tilt angle alpha of 2.60(15) degrees. The [1]silatrochrocenophane bearing the Me2Si bridge underwent facile and regioselective carbon-silicon bond cleavage with [Pt(PEt3)4] to give a very high yield of an oxidative addition product. The ring-opening polymerization of these novel [1]silatrochrocenophanes afforded ring-opened chromium-based polymers.

Journal Article↗
PubMed2006

Metallopolymer-peptide conjugates: synthesis and self-assembly of polyferrocenylsilane graft and block copolymers containing a beta-sheet forming Gly-Ala-Gly-Ala tetrapeptide segment.

We describe the synthesis and self-assembly of two beta-sheet forming metallopolymer-peptide conjugates. The ability of the oligotetrapeptide sequence Gly-Ala-Gly-Ala (GAGA) to form antiparallel beta-sheets was retained in PFS-b-AGAG (PFS = polyferrocenylsilane) and PFS-g-AGAG conjugates with block and graft architectures, respectively. In the solid state, DSC experiments suggest a phase separation between the peptide and PFS domains. In toluene, PFS-b-AGAG interestingly forms a fibrous network which consists of a core containing the self-assembled antiparallel beta-sheet peptide and a corona of organometallic PFS. The self-assembly of the peptide into antiparallel beta-sheets is the driving force for the fiber formation, whereas PFS prevents uncontrolled lateral aggregation of the fibers. The use of an oligopeptide to self-assemble an otherwise random coiled organometallic polymer may be a useful strategy to enhance nanostructure formation. In the cases described here, the conjugates may be used to create nanopatterned ceramics, and the redox properties of the resulting supramolecular aggregates are of significant interest.

Molecular Conformation↗
PubMed2005

Phosphorescence quenching of dyes adsorbed to silica thin-layer chromatography plates.

We describe photoluminescence (PL) quenching experiments by oxygen for a series of transition metal dyes adsorbed to commercial silica thin-layer chromatography plates. These TLC plates have been used by others as rapidly responding PL pressure sensors. The quenching kinetics show interesting differences from the behavior of the same dyes adsorbed to the more well-defined surfaces of SBA-15 mesoporous silica particles adsorbed to a thin layer-by-layer polymer film as reported in Chem. Mater. 2005, 17, 3160. The pore size and the pore size distribution are much larger for the TLC silica than for the mesoporous silica. On the TLC silica, the dye PL decay profiles show smaller deviations from an exponential form. One sees larger differences between the intensity and lifetime Stern-Volmer plots, and most surprisingly, the dyes on the surface of the TLC silica are about three times more sensitive to quenching by oxygen.

Journal Article↗
PubMed2005

Reversible skeletal transmetalations of inorganic rings: isolation of aluminatophosphazenes, a zwitterionic phosphazene, and a donor-stabilized alumazine-phosphazene hybrid cation.

Synthesis of the cyclic aluminatophosphazene ring N(PCl2NMe)2AlMeCl (5) has been achieved via a skeletal transmetalation reaction between AlMe3 and the boratophosphazene N(PCl2NMe)2BCl2 (1). Reaction of 5 with various halogenated Lewis acids such as GaCl3 yielded the fully chlorinated aluminum heterocycle N(PCl2NMe)2AlCl2 (8) through a methyl-halogen exchange process. In contrast, treatment of 5 with excess AlMe3 resulted in complete methylation at aluminum to give N(PCl2NMe)2AlMe2 (6). Compound 5 was reacted with various Ag+ salts with weakly coordinating anions, including Ag[OSO2CF3], which afforded the triflate-substituted heterocycle N(PCl2NMe)2AlMe(OSO2CF3) (9). The reaction of 5 with Ag[BF4] surprisingly produced the previously known fluorinated boratophosphazene N(PCl2NMe)2BF2 (10). The transformation of 1 to 5 and then to 10 represents a rare, formally reversible, skeletal transmetalation process involving boron and aluminum. Treatment of 5 with Ag[PF6] led to the insertion of phosphorus in place of aluminum to form the novel zwitterionic fluorinated phosphorus(V) heterocycle N(PCl2NMe)2PF4 (11). The ethyl-substituted aluminatophosphazene N(PCl2NMe)2AlMeEt (14) reacted cleanly with a 1:1 mixture of [Ph3C][B(C6F5)4] and THF to give the novel donor-stabilized alumazine-phosphazene hybrid cation, [7.THF]+, as the [B(C6F5)4]- salt [N(PCl2NMe)2AlMe.THF][B(C6F5)4] (15).

Journal Article↗
PubMed2005

Block copolymers under periodic, strong three-dimensional confinement.

In this communication we study the influence of strong 3D confinement on the self-assembly of diblock copolymers containing a polyferrocenylsilane metallopolymer segment. Both silica colloidal crystals and silica inverse colloidal crystals, having nanometer-scale interconnected pore networks, are used as molds to direct the self-assembly. Unusual morphologies, such as concentric shells and branched lamellae, result from the interaction of the polymer with the high surface area topologically periodic templates.

Journal Article↗
PubMed2005

Rhodium-catalyzed dehydrocoupling of fluorinated phosphine-borane adducts: synthesis, characterization, and properties of cyclic and polymeric phosphinoboranes with electron-withdrawing substituents at phosphorus.

The dehydrocoupling of the fluorinated secondary phosphine-borane adduct R2PH.BH3 (R = p-CF3C6H4) at 60 degrees C is catalyzed by the rhodium complex [{Rh(mu-Cl)(1,5-cod)}2] to give the four-membered chain R2PH-BH2-R2P-BH3. A mixture of the cyclic trimer [R2P-BH2]3 and tetramer [R2P-BH2]4 was obtained from the same reaction at a more elevated temperature of 100 degrees C. The analogous rhodium-catalyzed dehydrocoupling of the primary phosphine-borane adduct RPH2.BH3 at 60 degrees C gave the high molecular weight polyphosphinoborane polymer [RPH-BH2]n (Mw = 56,170, PDI = 1.67). The molecular weight was investigated by gel permeation chromatography and the compound characterized by multinuclear NMR spectroscopy. Interestingly, the electron-withdrawing fluorinated aryl substituents have an important influence on the reactivity as the dehydrocoupling process occurred efficiently at the mildest temperatures observed for phosphine-borane adducts to date. Thin films of polymeric [RPH-BH2]n (R = p-CF3C6H4) have also been shown to function as effective negative-tone resists towards electron beam (e-beam) lithography (EBL). The resultant patterned bars were characterized by scanning electron microscopy (SEM), atomic force microscopy (AFM) and time-of-flight secondary ion mass spectrometry (TOF-SIMS).

Journal Article↗
PubMed2005

Photochemically and thermally tunable planar defects in colloidal photonic crystals.

We report a bottom-up synthesis of a photochemically and thermally active azobenzene-based polyelectrolyte multilayer (PEM) planar defect embedded in a colloidal photonic crystal (CPC). Both photoisomerization and thermal cycling lead to a precise tuning of an intragap transmitting state induced by the PEM structural defect.

Journal Article↗
PubMed2005

Redox-induced synthesis and encapsulation of metal nanoparticles in shell-cross-linked organometallic nanotubes.

A new approach to encapsulate silver nanoparticles inside block copolymer nanotubes is reported and involves an in situ redox reaction between a polyferrocenylsilane (PFS) inner wall and silver ions. Partial preoxidation of the PFS domains was found to be a key step for the efficient formation of one-dimensional arrays of silver nanoparticles confined within the nanotubes.

Ferrous Compounds↗