Reactions of (-)-sparteine with alkali metal HMDS complexes : conventional meets the unconventional

Conventional (-)-sparteine adducts of lithium and sodium 1,1,1,3,3,3-hexamethyldisilazide (HMDS) were prepared and characterised, along with an unexpected and unconventional hydroxyl-incorporated sodium sodiate, [(-)-sparteine·Na(-HMDS)Na·(-)-sparteine]+[Na4(-HMDS)4(OH)]--the complex anion of which is the first inverse crown ether anion

Public HMDs: Modeling and Understanding User Behavior Around Public Head-Mounted Displays

Head-Mounted Displays (HMDs) are becoming ubiquitous; we are starting to see them deployed in public for different purposes. Museums, car companies and travel agencies use HMDs to promote their products. As a result, situations arise where users use them in public without experts supervision. This leads to challenges and opportunities, many of which are experienced in public display installations. For example, similar to public displays, public HMDs struggle to attract the passer-by's attention, but benefit from the honeypot effect that draws attention to them. Also passersby might be hesitant to wear a public HMD, due to the fear that its owner might not approve, or due to the perceived need for a prior permission. In this work, we discuss how public HMDs can benefit from research in public displays. In particular, based on the results of an in-the-wild deployment of a public HMD, we propose an adaptation of the audience funnel flow model of public display users to fit the context of public HMD usage. We discuss how public HMDs bring in challenges and opportunities, and create novel research directions that are relevant to both researchers in HMDs and researchers in public displays

I Am The Passenger: How Visual Motion Cues Can Influence Sickness For In-Car VR

This paper explores the use of VR Head Mounted Displays (HMDs) in-car and in-motion for the first time. Immersive HMDs are becoming everyday consumer items and, as they offer new possibilities for entertainment and productivity, people will want to use them during travel in, for example, autonomous cars. However, their use is confounded by motion sickness caused in-part by the restricted visual perception of motion conflicting with physically perceived vehicle motion (accelerations/rotations detected by the vestibular system). Whilst VR HMDs restrict visual perception of motion, they could also render it virtually, potentially alleviating sensory conflict. To study this problem, we conducted the first on-road and in motion study to systematically investigate the effects of various visual presentations of the real-world motion of a car on the sickness and immersion of VR HMD wearing passengers. We established new baselines for VR in-car motion sickness, and found that there is no one best presentation with respect to balancing sickness and immersion. Instead, user preferences suggest different solutions are required for differently susceptible users to provide usable VR in-car. This work provides formative insights for VR designers and an entry point for further research into enabling use of VR HMDs, and the rich experiences they offer, when travelling

The Use of Herbal Medications and Dietary Supplements by People with Mental Illness

This study examined the relationship between herbal medication and dietary supplement (HMDS) use and mental health characteristics. Data are drawn from a national household survey of the United States’ civilian, non-institutionalized population (N = 9,585). Psychiatric medication and HMDS use, psychiatric diagnoses and treatment needs, utilization and satisfaction were assessed. Compared to non-users, HMDS users were more likely to perceive themselves as having mental health needs, to have received mental health and primary care treatment, and to be dissatisfied with their overall healthcare. Psychiatric medication use was not related to HMDS use, and in multivariate analyses, HMDS use was associated with perceived mental health needs. Differences in use of specific HMDS between those with and without a psychiatric disorder were also examined. The use of HMDS warrants particular attention in persons with perceived mental health problems as these individuals may be turning to HMDS use for treatment of their symptoms

Structural studies of cesium, lithium/cesium and sodium/cesium bis(trimethylsilyl)amide (HMDS) complexes

Reacting cesium fluoride with an equimolar n-hexane solution of lithium bis(trimethylsilyl)amide (LiHMDS), allows the isolation of CsHMDS (1) in 80% yield (after sublimation). This preparative route to 1 negates the need for pyrophoric Cs metal or organocesium reagents in its synthesis. If a 2:1 LiHMDS:CsF ratio is employed the heterobimetallic polymer [LiCs(HMDS)2]∞ 2 was isolated (57% yield). By combining equimolar quantities of NaHMDS and CsHMDS in hexane/toluene [NaCs(HMDS)2(toluene)]∞ 3 was isolated (62% yield). Attempts to prepare the corresponding potassium-cesium amide failed, and instead yielded the known monometallic polymer [Cs(HMDS)(toluene)]∞ 4. With the aim of expanding the structural diversity of Cs(HMDS) species, 1 was reacted with several different Lewis basic donor molecules of varying denticity; namely, (R,R)-N,N,N′,N′-tetramethylcyclohexane-1,2-diamine [(R,R)-TMCDA] and N,N,Nʹ,Nʹ-tetramethylethylenediamine (TMEDA), N,N,Nʹ,Nʹʹ,Nʹʹ-pentamethyldiethylenetriamine (PMDETA), tris[2-(dimethylamino)ethyl]amine (Me6-TREN) and tris[2-(2-methoxyethoxy)ethyl]amine (TMEEA). These reactions yielded dimeric [Cs(HMDS)·donor]2 5-7 [where donor is (R,R)-TMCDA, TMEDA and PMDETA respectively], the tetranuclear ‘open’-dimer [{Me6-TREN·Cs(HMDS)}2{Cs(HMDS)}2] 8 and the monomeric Cs(HMDS)·TMEEA 9. Complexes 2,3 and 5-9 were characterized by X-ray crystallography and in solution by multinuclear NMR spectroscopy

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

Accessing Sodium Ferrate complexes containing neutral and anionic N-heterocyclic carbene ligands : structural, synthetic, and magnetic insights

This study reports the synthesis and single-crystal X-ray crystallographic, NMR spectroscopic, and magnetic characterization of a series of sodium ferrates using bis(amide) Fe(HMDS)2 as a precursor (HMDS = 1,1,1,3,3,3-hexamethyldisilazide). Reaction with sodium reagents NaHMDS and NaCH2SiMe3 in hexane afforded donor-solvent-free sodium ferrates [{NaFe(HMDS)3}∞] (1) and [{NaFe(HMDS)2(CH2SiMe3)}∞] (2), respectively, which exhibit contacted ion pair structures, giving rise to new polymeric chain arrangements made up of a combination of inter- and intramolecular Na···Me(HMDS) electrostatic interactions. Addition of the unsaturated NHC IPr (IPr = 1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene) to 1 and 2 caused deaggregation of their polymeric structures to form discrete NHC-stabilized solvent-separated ion pairs [Na(IPr)2]+[Fe(HMDS)3]- (3) and [(THF)3·NaIPr]+[Fe(HMDS)2CH2SiMe3]- (4), where in both cases, the NHC ligand coordinates preferentially to Na. In contrast, when IPr is sequentially reacted with the single-metal reagents NaCH2SiMe3 and Fe(HMDS)2, the novel heteroleptic ferrate (THF)3Na[:C{[N(2,6-iPr2C6H3)]2CHCFe(HMDS)2}] (5) is obtained. This contains an anionic NHC ligand acting as an unsymmetrical bridge between the two metals, coordinating through its abnormal C4 position to Fe and its normal C2 position to Na. The formation of 5 can be described as an indirect ferration process where IPr is first metalated at the C4 position by the polar sodium alkyl reagent, which in turn undergoes transmetalation to the more electronegative Fe(HMDS)2 fragment. Treatment of 5 with 1 molar equiv of methyl triflate (MeOTf) led to the isolation and structural elucidation of the neutral abnormal NHC (aNHC) tricoordinate iron complex [CH3C{[N(2,6-iPr2C6H3)]2CHCFe(HMDS)2}] (6) with the subsequent elimination of NaOTf, disclosing the selectivity of complex 5 to react with this electrophile via its C2 position, leaving its Fe-C4 and Fe-N bonds intact. The magnetic susceptibility properties of compounds 1-6 have been examined. This study revealed a drastic change of magnetic susceptibility in replacing a pure σ donor from an idealized trigonal coordination environment by an NHC π donating character