Catalytic C-H bond amination from high-spin iron imido complexes

Dipyrromethene ligand scaffolds were synthesized bearing large aryl (2,4,6-Ph(3)C(6)H(2), abbreviated Ar) or alkyl ((t)Bu, adamantyl) flanking groups to afford three new disubstituted ligands ((R)L, 1,9-R(2)-5-mesityldipyrromethene, R=aryl, alkyl). While high-spin (S=2), four-coordinate iron complexes of the type ((R)L)FeCl(solv) were obtained with the alkyl-substituted ligand varieties (for R=(t)Bu, Ad and solv=THF, OEt(2)), use of the sterically encumbered aryl-substituted ligand precluded binding of solvent and cleanly afforded a high-spin (S=2), three-coordinate complex of the type ((Ar)L)FeCl. Reaction of ((Ad)L)FeCl(OEt(2)) with alkyl azides resulted in the catalytic amination of C-H bonds or olefin aziridination at room temperature. Using a 5% catalyst loading, 12 turnovers were obtained for the amination of toluene as a substrate, while greater than 85% of alkyl azide was converted to the corresponding aziridine employing styrene as a substrate. A primary kinetic isotope effect of 12.8(5) was obtained for the reaction of ((Ad)L)FeCl(OEt(2)) with adamantyl azide in an equimolar toluene/toluene-d(8) mixture, consistent with the amination proceeding through a hydrogen atom abstraction, radical rebound type mechanism. Reaction of p-(t)BuC(6)H(4)N(3) with ((Ar)L)FeCl permitted isolation of a high-spin (S=2) iron complex featuring a terminal imido ligand, ((Ar)L)FeCl(N(p-(t)BuC(6)H(4))), as determined by (1)H NMR, X-ray crystallography, and (57)Fe Mo?ssbauer spectroscopy. The measured Fe-N(imide) bond distance (1.768(2) ?) is the longest reported for Fe(imido) complexes in any geometry or spin state, and the disruption of the bond metrics within the imido aryl substituent suggests delocalization of a radical throughout the aryl ring. Zero-field (57)Fe Mo?ssbauer parameters obtained for ((Ar)L)FeCl(N(p-(t)BuC(6)H(4))) suggest a Fe(III) formulation and are nearly identical with those observed for a structurally similar, high-spin Fe(III) complex bearing the same dipyrromethene framework. Theoretical analyses of ((Ar)L)FeCl(N(p-(t)BuC(6)H(4))) suggest a formulation for this reactive species to be a high-spin Fe(III) center antiferromagnetically coupled to an imido-based radical (J = -673 cm(-1)). The terminal imido complex was effective for delivering the nitrene moiety to both C-H bond substrates (42% yield) as well as styrene (76% yield). Furthermore, a primary kinetic isotope effect of 24(3) was obtained for the reaction of ((Ar)L)FeCl(N(p-(t)BuC(6)H(4))) with an equimolar toluene/toluene-d(8) mixture, consistent with the values obtained in the catalytic reaction. This commonality suggests the isolated high-spin Fe(III) imido radical is a viable intermediate in the catalytic reaction pathway. Given the breadth of iron imido complexes spanning several oxidation states (Fe(II)-Fe(V)) and several spin states (S=0→(3)/(2)), we propose the unusual electronic structure of the described high-spin iron imido complexes contributes to the observed catalytic reactivity.     

EQUITY ISSUES AFFECTING MATHEMATICS LEARNING USING ICT

Our concern is the inequities that arise from differential access and use of educational technology in mathematics for groups characterised by gender, ethnicity, income level and ability. As access to information and communications technology (ICT) increases both in homes and schools, our paper asks whether previous inequities are being ironed out or exacerbated. Equity is considered from the three perspectives proposed by Fennema (1990), namely in terms of: (a) opportunities to learn (physical access); (b) educational treatment (how technology is used, by whom), and the social and psychological factors influencing its use; (c) educational outcomes (impacts on achievement, attitudes and motivation). Suggested policies and pedagogies for removing the boundaries between technology ‘haves’ and ‘have-nots’ are presented.     

Significance of grafting in curing processes initiated by UV, excimer and ionising radiation sources

The grafting of a typical methacrylate monomer (MMA) to polypropylene (PPE) and cellulose initiated by UV and ionising radiation is reported. The effect of additives which constitute components in radiation curing on the grafting process is examined. Additives studied include photoinitiators (PIs), multifunctional acrylates and methacrylates and acrylate oligomers. Synergistic effects when these additives are combined in the same solution are reported. The photografting studies have been extended to include grafting with charge transfer (CT) complexes involving donor/acceptor (DA) monomers to PPE, cellulose and wool. The importance of this work in conventional and PI free curing is discussed, particularly the significance of concurrent grafting during curing.     

Understanding delamination in microelectronic devices using AES,XPS and chemometrics

The recent development of XPS instrumentation with near‐micron spatial resolution has advanced the capability of elemental and chemical‐state imaging accompanied by small‐area analysis (down to 15 µm). In this paper, the combined use of X‐ray photoelectron spectroscopy (XPS) and Auger electron spectroscopy (AES) at enhanced spatial resolution is shown to have significantly improved the understanding of interfacial delamination and related problems encountered in the production of electronic devices in the field of microelectronics. An example of the application of surface analysis for ITO/Mo adhesion problems will be presented. The mathematical procedure using principal component analysis (PCA) in the reduction of noise in XPS images will also be described. The dramatic improvements in the image contrast and chemical component determination from multispectral image data sets will be presented. This study is intended to explore the contributions given by advanced surface analysis tools to solve real‐world problems. Copyright © 2007 John Wiley & Sons, Ltd.     

In Situ Deprotection and Incorporation of Unnatural Amino Acids during Cell‐Free Protein Synthesis

The S30 extract from E. coli BL21 Star (DE3) used for cell‐free protein synthesis removes a wide range of α‐amino acid protecting groups by cleaving α‐carboxyl hydrazides; methyl, benzyl, tert‐butyl, and adamantyl esters; tert‐butyl and adamantyl carboxamides; α‐amino form‐, acet‐, trifluoroacet‐, and benzamides; and side‐chain hydrazides and esters. The free amino acids are produced and incorporated into a protein under standard conditions. This approach allows the deprotection of amino acids to be carried out in situ to avoid separate processing steps. The advantages of this approach are demonstrated by the efficient incorporation of the chemically intractable (S)‐4‐fluoroleucine, (S)‐4,5‐dehydroleucine, and (2S,3R)‐4‐chlorovaline into a protein through the direct use of their respective precursors, namely, (S)‐4‐fluoroleucine hydrazide, (S)‐4,5‐dehydroleucine hydrazide, and (2S,3R)‐4‐chlorovaline methyl ester. These results also show that the fluoro‐ and dehydroleucine and the chlorovaline are incorporated into a protein by the normal biosynthetic machinery as substitutes for leucine and isoleucine, respectively.     

Evidence for Rydberg doorway states in photoion pair formation in bromomethane

The vacuum ultraviolet laser-excited photoion-pair formation spectrum of CH 3Br has been measured under high resolution in the threshold region. The (2 + 1) and (3 + 1) resonance-enhanced multiphoton ionization spectra in the same energy region are also reported. By comparison of the spectra in this and a more extended region, resonances in the photoion-pair formation spectrum are assigned to p and f Rydberg states. It is concluded that all the structure in the photoion-pair formation spectrum near threshold can be accounted for by members of the Omega = 0 subset of Rydberg states that act as doorway states to the ion channel.     

Riordan arrays and the LDU decomposition of symmetric Toeplitz plus Hankel matrices

We examine a result of Basor and Ehrhardt concerning Hankel and Toeplitz plus Hankel matrices, within the context of the Riordan group of lower-triangular matrices. This allows us to determine the LDU decomposition of certain symmetric Toeplitz plus Hankel matrices. We also determine the generating functions and Hankel transforms of associated sequences.     

Magnesium isotope ratio measurements by negative thermal ionisation mass spectrometry using molecular fluoride ions

A new technique for accurate Mg isotope ratio measurements has been developed with MgF₂ as sample compound. With the help of a fluorinating agent negatively charged MgF₃ molecular ions were formed in the ion source of a thermal ionisation mass spectrometer. An evaporation study has been performed and the results clearly show that Mg is evaporated from the filament as MgF₂ molecules. The MgF₂ technique has been applied in the certification of a candidate ²⁶Mg-enriched Spike Isotope Reference Material. The result from this new technique has been compared with results obtained for the same material using ICP-MS.     

The role of the graphic calculator in mediating graphing activity

The PIGMI (Portable Information Technologies for supporting Graphical Mathematics Investigations) Project ¹ investigated the role of portable technologies in facilitating development of students' graphing skills and concepts. This paper examines the impact of a recent shift towards calculating and computing tools as increasingly accessible, everyday technologies on the nature of learning in a traditionally difficult curriculum area. The paper focuses on the use of graphic calculators by undergraduates taking an innovative new mathematics course at the Open University. A questionnaire survey of both students and tutors was employed to investigate perceptions of the graphic calculator and the features which facilitate graphing and linking between representations. Key features included visualization of functions, immediate feedback and rapid graph plotting. A follow-up observational case study of a pair of students illustrated how the calculator can shape mathematical activity, serving a catalytic, facilitating and checking role. The features of technology-based activities which can structure and support collaborative problem solving were also examined. In sum, the graphic calculator technology acted as a critical mediator in both the students' collaboration and in their problem solving. The pedagogic implications of using portables are considered, including the tension between using and over-using portables to support mathematical activity.