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Editorial
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Two alternative approaches to access mixed hydride-amido zinc complexes : synthetic, structural and solution implications
Using bis(amide) Zn(HMDS)2 (HMDS = 1,1,1,3,3,3-hexamethyldisilazide) as a precursor, this study explores the synthesis of N-heterocyclic carbene stabilized mixed amido-hydride zinc complexes using two alternative hydride sources, namely dimethylamine borane (DMAB) and phenylsilane PhSiH3. Hydride-rich zinc cluster Zn4(HMDS)2H6·2IPr (1) (IPr = 1,3-bis(2,6-di-isopropylphenyl)imidazol-2-ylidene), which can be envisaged as a co-complex of IPr·ZnH2 and (HMDS)ZnH, is obtained when DMAB is employed, with the concomitant formation of heteroleptic bis(amido)borane [HB(NMe2)(HMDS)] and H2 evolution. NMR studies in d8-THF show that although the bulky carbene IPr does not bind to the zinc bis(amide), its presence in the reaction media is required in order to stabilise 1. Reactions using the slightly less sterically demanding NHC IXy (IXy = 1,3-bis-(2,6-dimethylphenyl)imidazol-2-ylidene) led to the isolation and structural elucidation of the carbene adduct Zn(HMDS)2·IXy (2). Contrastingly, mixtures of equimolar amounts of PhSiH3 and the zinc bis(amide) (60 °C, 3 h, hexane) afforded monomeric heteroleptic hydride (HMDS)ZnH·IPr (3). NMR studies, including DOSY experiments, revealed that while the integrity of 3 is retained in polar d8-THF solutions, in lower polarity C6D6 it displays a much more complex solution behaviour, being in equilibrium with the homoleptic species ZnH2·IPr, Zn(HMDS)2 and IPr
The diverse world of career guidance
This book is the product of an EU funded project involving parterns from The Czech Republic, Denmark and the United Kingdom. The book contains personal reflections of career guidance provision and activities in which theory and practice are united through the eyes of experienced practitioners from a range of guidance settings. This book is aimed at both established and new guidance practitionersEU Erasmus
Stimulated superconductivity at strong coupling
Stimulating a system with time dependent sources can enhance instabilities,
thus increasing the critical temperature at which the system transitions to
interesting low-temperature phases such as superconductivity or superfluidity.
After reviewing this phenomenon in non-equilibrium BCS theory (and its marginal
fermi liquid generalization) we analyze the effect in holographic
superconductors. We exhibit a simple regime in which the transition temperature
increases parametrically as we increase the frequency of the time-dependent
source.Comment: 19 pages, 2 figure. v3: Comments, references and one figure added.
Version to appear in JHE
A massive proto-cluster of galaxies at a redshift of z {\approx} 5.3
Massive clusters of galaxies have been found as early as 3.9 Billion years
(z=1.62) after the Big Bang containing stars that formed at even earlier
epochs. Cosmological simulations using the current cold dark matter paradigm
predict these systems should descend from "proto-clusters" - early
over-densities of massive galaxies that merge hierarchically to form a cluster.
These proto-cluster regions themselves are built-up hierarchically and so are
expected to contain extremely massive galaxies which can be observed as
luminous quasars and starbursts. However, observational evidence for this
scenario is sparse due to the fact that high-redshift proto-clusters are rare
and difficult to observe. Here we report a proto-cluster region 1 billion years
(z=5.3) after the Big Bang. This cluster of massive galaxies extends over >13
Mega-parsecs, contains a luminous quasar as well as a system rich in molecular
gas. These massive galaxies place a lower limit of >4x10^11 solar masses of
dark and luminous matter in this region consistent with that expected from
cosmological simulations for the earliest galaxy clusters.Comment: Accepted to Nature, 16 Pages, 6 figure
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