Metal complexes as potential ligands : the deprotonation of aminephenolate metal complexes

The cationic nickel, copper and zinc complexes of tris-(2-hydroxybenzyl)-aminoethylamine (H6TrenSal) have been deprotonated using potassium hydroxide. The nickel complex can be sequentially deprotonated to form a series of compounds namely, [(H6TrenSal)Ni]+, [(H6TrenSal)Ni] and "[(H6TrenSal)Ni]K". The latter is isolated as a mixture of species namely [{(H6TrenSal)Ni}K(EtOH)]2, [{(H6TrenSal)Ni}K(EtOH)2-μ-OH2]2 and [{(H6TrenSal)Ni}K(EtOH)2-μ-EtOH]2, which co-crystallise in a roughly 50:27.5:22.5 ratio. In contrast the deprotonation of [(H6TrenSal)M]+ (M = Cu, Zn) results in the formation of tetrameric complexes [({(H6TrenSal)Ni}K(OH2)2)4(μ4-OH2)]

Diisopropylamide and TMP turbo-grignard reagents : a structural rationale for their contrasting reactivities

A neutral dimeric molecule in crystal form, the diisopropylamido turbo-Grignard reagent "(iPr2N)MgCl⋅LiCl" (see structure; blue N, red O, green Mg, yellow Cl, black C) separates into several charged ate species in dynamic exchange with each other in THF solution as determined by a combination of EXSY and DOSY NMR studies

Twisted [(R3P)PdX] groups above dicarbaborane ligands: 4-dimethylsulfido-3-iodo-3-triphenylphosphine-closo-3-pallada-1,2-dicarbadodecaborane and 3-dimethylphenylphosphine-3-chloro-4-dimethylsulfido-closo-3-pallada-1,2-dicarbadodecaborane

The structural analyses of [3-(PPh₃)-3-I-4-(SMe₂)-closo-3,1,2-PdC₂B₉H₁₀] or [Pd(C₄H₁₆B₉S)I(C₁₈H₁₅P)], (I), and [3-(PPhMe₂)-3-Cl-4-(SMe₂)-closo-3,1,2-PdC₂B₉H₁₀] or [Pd(C₄H₁₆B₉S)Cl(C₈H₁₁P)], (II), show that in comparison with [3-(PR₃)2-closo-3,1,2-PdC₂B₉H₁₁] the presence of the 4-SMe₂ group causes the [PdX(PR₃)] unit (X = halogen) to twist about an axis passing through the Pd atom and the directly opposite B atom of the carbaborane ligand. The halogen atoms are located almost directly above a C atom in the C₂B₃ face, and the conformations of the [PdX(PR₃)] units above the C₂B₃ faces are not those predicted from molecular orbital calculations of the closo-3,1,2-PdC₂B₉ system. The fact that the variation from the predicted conformation is greater in the case of (I) than in (II) may be ascribed to the greater steric interactions induced by the I atom in (I) compared with the Cl atom in (II)

[NASA/DOD Aerospace Knowledge Diffusion Research Project. Paper 2:] External Information Sources and aerospace R&D: The use and importance of technical reports by US aerospace engineers and scientists

This paper formulates and studies two propositions. Proposition 1 states that information that is external to the aerospace organization tends to be used less than internal sources of information; the more geographically removed the information is from the organization, the less likely it is to be used. Proposition 2 states that of the various sociometric variables assumed to influence the use of an information channel or source, perceived accessibility exerts the greatest influence. Preliminary analysis based on surveys supports Proposition 1. This analysis does not support Proposition 2, however. Evidence here indicates that reliability and relevance influence the use of an information source more than the idea of perceived accessibility

Tetradentate Schiff base beryllium complexes

The structure of (BeSalen)2 is reported. The incompatibility of the geometry of the beryllium with the inflexibility of the Salen ligand gives rise to a rare dimeric bis-didentate motif

Spatially Resolved Images of Dust Belt(s) Around the Planet-hosting Subgiant Kappa CrB

We present Herschel spatially resolved images of the debris disc orbiting the subgiant Kappa CrB. Not only are these the first resolved images of a debris disc orbiting a subgiant, but Kappa CrB is a rare example of an intermediate mass star where a detailed study of the structure of the planetary system can be made, including both planets and planetesimal belt(s). The only way to discover planets around such stars using the radial velocity technique is to observe 'retired' A stars, which are cooler and slower rotators compared to their main-sequence counterparts. A planetary companion has already been detected orbiting the subgiant Kappa CrB, with revised parameters of m sin i = 2.1MJ and apl = 2.8AU (Johnson et al. 2008a). We present additional Keck I HIRES radial velocity measurements that provide evidence for a second planetary companion, alongside Keck II AO imaging that places an upper limit on the mass of this companion. Modelling of our Herschel images shows that the dust is broadly distributed, but cannot distinguish between a single wide belt (from 20 to 220AU) or two narrow dust belts (at around 40 and 165AU). Given the existence of a second planetary companion beyond approximately 3AU it is possible that the absence of dust within approximately 20AU is caused by dynamical depletion, although the observations are not inconsistent with depletion of these regions by collisional erosion, which occurs at higher rates closer to the star.Comment: Updated abstrac

Prevalence of qacA/B genes and mupirocin resistance among methicillin-resistant Staphylococcus aureus (MRSA) isolates in the setting of chlorhexidine bathing without mupirocin

OBJECTIVE: We aimed to determine the frequency of qacA/B chlorhexidine tolerance genes and high-level mupirocin resistance among MRSA isolates before and after the introduction of a chlorhexidine (CHG) daily bathing intervention in a surgical intensive care unit (SICU). DESIGN: Retrospective cohort study (2005–2012) SETTING: A large tertiary-care center PATIENTS: Patients admitted to SICU who had MRSA surveillance cultures of the anterior nares METHODS: A random sample of banked MRSA anterior nares isolates recovered during (2005) and after (2006–2012) implementation of a daily CHG bathing protocol was examined for qacA/B genes and high-level mupirocin resistance. Staphylococcal cassette chromosome mec (SCCmec) typing was also performed. RESULTS: Of the 504 randomly selected isolates (63 per year), 36 (7.1%) were qacA/B positive ( + ) and 35 (6.9%) were mupirocin resistant. Of these, 184 (36.5%) isolates were SCCmec type IV. There was a significant trend for increasing qacA/B (P= .02; highest prevalence, 16.9% in 2009 and 2010) and SCCmec type IV (P< .001; highest prevalence, 52.4% in 2012) during the study period. qacA/B( + ) MRSA isolates were more likely to be mupirocin resistant (9 of 36 [25%] qacA/B( + ) vs 26 of 468 [5.6%] qacA/B(−); P= .003). CONCLUSIONS: A long-term, daily CHG bathing protocol was associated with a change in the frequency of qacA/B genes in MRSA isolates recovered from the anterior nares over an 8-year period. This change in the frequency of qacA/B genes is most likely due to patients in those years being exposed in prior admissions. Future studies need to further evaluate the implications of universal CHG daily bathing on MRSA qacA/B genes among hospitalized patients