The strong organoborane Lewis acid B(C6F5)3 catalyzes the hydrosilation (using R3SiH) of aromatic and aliphatic carbonyl functions at convenient rates with loadings 1−4%. For aldehydes ketones, product silyl ethers are isolated in 75−96% yield; for esters, produced upon workup acetal products can be obtained 45−70% yield. Extensive mechanistic studies point to an unusual silane activation mechanism rather than one involving borane function. Quantitative kinetic show that least basic...

A broad range of benzaldimines and ketimines can be hydrosilated efficiently, employing B(C(6)F(5))(3) as a catalyst in conjunction with PhMe(2)SiH. Spectral evidence supports the intermediacy silyliminium cation hydridoborate counterion formed via abstraction hydride from PhMe(2)SiH by presence imines.

The commercially available borane tris(pentafluorophenyl)borane, B(C(6)F(5))(3), is an effective catalyst for the dehydrogenative silation of alcohols using a variety silanes, R(3)SiH, R(2)SiH(2), and R(2)R'SiH. Generally, reactions occur in convenient time frame at room temperature 2 mol % are clean high yielding, with dihydrogen as only byproduct. Primary aliphatic silated cleanly but slowly, reaction times ranging from 20 to 144 h. Faster can be achieved by increasing loading 8 or heating...

Abstract Over the last 30 years, governments have sought to give citizens greater choice and control of public services they utilise. As a result, we seen creation various forms sector markets, including through contracting tendering processes and, more recently, by utilising individualised or ‘personalised’ care budgets. Under latter, individuals are given money purchase that meet their needs. There is growing evidence personalisation schemes may actually be entrenching administrative...

The reactions of AlMe3, BEt3, and ZnEt2 with toluene solutions the copper(II) complexes [CuL2] {L = acetylacetonate (acac; 1), hexafluoroacetylacetonate (hfac; 2), N-isopropyl-β-ketiminate (acnac; 3), N,N-dimethyl-β-diketiminate (nacnac; 4), 2-pyrrolylaldehyde (PyrAld; 5), N-isopropyl-2-pyrrolylaldiminate (PyrImiPr; 6a), N-ethyl-2-pyrrolylaldiminate (PyrImEt; 6b), N-isopropyl-2-salicylaldiminate (IPSA; 7)} were investigated, most combinations found to deposit metal films or powder at 50 °C...

Adducts of the N-benzyl imines Ph(R)CNBn (R = Ph, CH3, H) and tBu(CH3)CNBn N-phenyl imine Ph(H)CNPh with Lewis acid tris(pentafluorophenyl)borane, B(C6F5)3, have been prepared characterized in solution solid state. For each imine, is N-bound, exception sterically demanding base tBu(CH3)CNBn, which reacts B(C6F5)3 through its enamine tautomer to form an α-C bound adduct, 5. In N-bound imine−borane adducts 1−4, steric crowding π-stacking between C6F5 C6H5 rings results restricted rotation...

[structure: see text] The selective, B(C6F5)3-catalyzed allylstannation of aldehydes with proximal donor groups is shown to proceed via borane abstraction the allyl group from tin reagent and activation substrate by "Bu3Sn+". This supported a number 19F NMR experiments. selectivity reaction not attributable hypercoordinate boron as proposed discoverers this highly selective but likely involves chelation at tin.

A new synthetic route utilizes the reductive coupling of molybdenum(IV) acetylides toward construction both enediyne molecules and trialkoxymolybdenum alkylidynes, latter being useful as alkyne metathesis initiators. The molybdaziridine hydride complex Mo(H)(η2-Me2CNAr)(N[i-Pr]Ar)2, 1, readily prepared from MoCl3(thf)3, is elaborated in three generally high-yielding steps to enediynes and/or catalysts.

Mechanistic studies on the B(C(6)F(5))(3) catalyzed allylstannation of isomeric substituted benzaldehydes are reported. Confirming a report by Maruoka et al., good (5:1) to excellent (>20:1) selectivities for ortho over para isomers observed when 1:1 mixtures (X = OMe, Cl, F, OTBS) allylstannated with C(3)H(5)SnBu(3) in presence (2.5% per CHO). The best anisaldehydes. Multinuclear NMR solutions and (1:1 1:5) show that borane abstracts allyl group from organotin reagent, forming an adduct...

The solution reactions of bis(N-isopropylpyrrolylaldiminate)copper(II) (CuL2) with AlMe3, BEt3, and ZnEt2 have been studied. In all cases, reduction occurs in two stages via a stable copper(I) pyrrolylaldiminate complex (Cu2L2), each stage initiated by copper alkyl formation. Reduction from "LCuR" (R = Me or Et) release R2 L−R, consistent bimolecular C−C C−N bond-forming reductive elimination. At room temperature below, deposition "CuMe" exclusively elimination ethane, whereas decomposition...

A free phosphine/thioether/borane ligand (5) suitable to position a Lewis acidic borane in close proximity coordinated late transition metal has been prepared. Reaction with 0.5 [Pd2(dba)3] gave zwitterionic palladium(II) η3-boratoxypentadienyl complex the empirical formula [Pd(dba)(5)].

We directly compared ensemble spectroscopic measurements to a statistically rigorous single molecule electrical characterization of individual SWNT devices using high throughput probe station and reported, for the first time, highly accurate extinction coefficient ratio metallic semiconducting SWNTs 0.352 ± 0.009. The systematic counting types from solution also allows us examine variances associated with device properties therefore provide measure potential defect generation during...

A molecule that releases the strong organometallic Lewis acid B(C(6)F(5))(3) upon irradiation with 254 nm light has been developed. This photo generator (PhLAG) now enables photocontrolled initiation of several reactions catalyzed by this important acid. Herein is described synthesis triphenylsulfonium salt a carbamato borate based on carbazole function, its establishment as PhLAG, and application photorelease to fabrication thin films polysiloxane material.

This work advances a computational framework to probe the molecular inhomogeneities that occur in chemically amplified photoresists intended for ultraviolet (EUV) lithography. Atomistic dynamics simulations were used effect of ionic and steric interactions on dispersibility photoacid generators (PAGs) polymer medium before EUV exposure, as poor is potential source postexposure feature roughness. The PAGs studied include salts containing triphenyl sulfonium (TPS) cation with trifluoromethane...

Recently, both PSI¹ and ASML² illustrated champion EUVL resolution using slow, non-chemically amplified inorganic resists. However, the requirements for manufacturing require simultaneous delivery of high resolution, good sensitivity, low line edge/width roughness (LER/LWR) on commercial grade hardware. As a result, we believe that new classes materials should be explored understood. This paper focuses our efforts to assess metal oxide based nanoparticles as novel EUV...

Reaction between the potassium salts of hydro-tris-pyrazolylborate ligands Tp Me ' and tBu tris THF adduct scandium trichloride lead to isolation complexes (Tp Me,Me )ScCl 2 (THF), 1a, tBu,Me , 1b, in 65 49% yield, respectively. Subsequent reactions 1a 1b alkyl lithium reagents RLi (R = Me, CH SiMe 3 CH(SiMe ) gave as major isolated products all cases but one. The complex )Sc(CH 2a, could be obtained contaminated with at least 10% Li via this methodology. A salt-free alkane elimination route...

Extreme ultraviolet (EUV) lithography has gained momentum as the method of choice for <32-nm half-pitch device fabrication. In this paper, we describe our initial attempts to increase an EUV resist's sensitivity without compromising resolution and line roughness via introduction a thermally crosslinkable underlayer. The main purpose is test possibility using combination photoacid generators (PAGs) sensitizers (phenol type) in underlayer designs enhance overall performance resists. We have...

Resists are needed to advance extreme ultraviolet (EUV) lithography. In EUV resists, due the high energy of incident photons, most chemistry arises from emitted primary and secondary electrons not photons themselves. Because playing a leading role in patterning, initiating chemical transformations, it is important characterize their generation, transport, distribution. this work, we present several experimental techniques probe model polymer materials investigate impact specific groups on...

An improved protocol for the construction of substituted indenones is presented. Also effect substitution on intramolecular Friedel–Crafts acylation was noted. Specifically, if there no at 2-position indenone poor yields cyclized material were obtained, all, while a methyl or ethyl group greatly yield material. Placement large (e.g., benzyl) resulted in diminuation yield. The new synthetic procedure could, principle, allow 2,3-disubstituted indenones. One example this reaction mode

Nanoscale patterning of organic thin films is great interest for next-generation technologies. To keep pace with the demands state-of-the-art lithography, both sensitivity and resolution patternable need to be improved. Here we report a highly sensitive polyurea film grown by bottom-up assembly via molecular layer deposition (MLD) technique, which allows high-resolution at nanoscale. The MLD process used in this work provides an exceptionally high degree control over thickness composition...

193 nm light as an excitation source for resist patterning is limited due to the inability achieve pitch division much below limits of λ/2. Current techniques are examining use a variety photochemical manipulations means extend lithographic small, more defined images. Double patterning, or dual tone lithography, has recently garnered considerable interest potential two features within one exposure. In this contribution, single component carbamate photoacid/photobase (PAG/PBG) generators...

Extreme ultraviolet lithography (EUVL) technology continues to progress and remains a viable candidate for next generation lithography1, which drives the need EUV resists capable of high resolution with sensitivity low LWR. While chemically amplified (CARs) have demonstrated ability pattern 12nm half-pitch features2, collapse limit their ultimate resolution. We taken multiple approaches extend resist capabilities past these limits. Recent results in mitigation using encapsulation etch back...