Welcoming Neighbour or Inhospitable Host? Selective Second Metal Binding in 5- and 6-Phospha-Substituted Bpy Ligands.

The controlled formation of mixed-metal bimetallics was realised through use of a fac-[Re(CO)3(N,N'-bpy-P)Cl] complex bearing an exogenous 2,4,6-trioxa-1,3,5,7-tetramethyl-8-phosphaadamantane donor at the 5-position of the bpy. The introduction of gold, silver, and rhodium with appropriate secondary ligands was readily achieved from established starting materials. Restricted rotation about the C(bpy)-P bond was observed in several of the bimetallic complexes and correlated with the relative steric bulk of the second metal moiety. Related chemistry with the 6-substituted derivative proved more limited in scope with only the bimetallic Re/Au complex being isolated.

East Asian summer monsoon delivers large abundances of very-short-lived organic chlorine substances to the lower stratosphere.

Deep convection in the Asian summer monsoon is a significant transport process for lifting pollutants from the planetary boundary layer to the tropopause level. This process enables efficient injection into the stratosphere of reactive species such as chlorinated very-short-lived substances (Cl-VSLSs) that deplete ozone. Past studies of convective transport associated with the Asian summer monsoon have focused mostly on the south Asian summer monsoon. Airborne observations reported in this work identify the East Asian summer monsoon convection as an effective transport pathway that carried record-breaking levels of ozone-depleting Cl-VSLSs (mean organic chlorine from these VSLSs ~500 ppt) to the base of the stratosphere. These unique observations show total organic chlorine from VSLSs in the lower stratosphere over the Asian monsoon tropopause to be more than twice that previously reported over the tropical tropopause. Considering the recently observed increase in Cl-VSLS emissions and the ongoing strengthening of the East Asian summer monsoon under global warming, our results highlight that a reevaluation of the contribution of Cl-VSLS injection via the Asian monsoon to the total stratospheric chlorine budget is warranted.

Exploring Neurocognitive Performance Differences in Military Aviation Personnel.

INTRODUCTION: Military aeromedical evaluations are common, but specialized neuropsychological norms for aviation personnel are sparse, resulting in a need to rely on norms from the general population. Little has been published regarding aviation subpopulations and how their neuropsychological profiles may differ from general population normative data. This study investigated neuropsychological test results of aeromedical service members to evaluate consistency with general population norms, and to delineate differences between aviation subpopulations.METHODS: Analyses were conducted on demographic variables and test scores of military aviators (N 26) and nonaviator crewmembers (N 36) referred for evaluation due to a clinical problem requiring a waiver for flight status. Performance differences between subsamples were investigated with general linear modeling. Base rates for low scores were described.RESULTS: Mean test scores in both subsamples were 0 to 1 standard deviation (SD) above the general populations means, with the largest discrepancies being found on measures of visuospatial ability (crewmembers) and verbal learning (aviators). Modeling revealed a significant difference between aviators and crewmembers on Trail Making Test Part B, after accounting for education. Aviators produced fewer low scores than crewmembers, even when using education adjusted normative data.DISCUSSION: Results suggest the cognitive profile of aviators is uniquely strong in specific domains, with fewer low scores. The development of aviator-specific norms may enhance sensitivity to cognitive decrements in this population. Future studies might separately assess crewmember roles to further assess cognitive performance standards across specialties.Maltez-Laurienti A, Minniear A, Moore R, McGovern T, Newman P, Brearly T. Exploring neurocognitive performance differences in military aviation personnel. Aerosp Med Hum Perform. 2021; 92(9):702709.

Remote control: stereoselective coordination of electron-deficient 2,2'-bipyridine ligands to Re(I) and Ir(III) cores.

Highly diastereoselective coordination of unsymmetrical cationic 2,2'-bipyridine ligands bearing a chiral amidinium substituent to [Re(CO)3Cl] and [Ir(PhPy)2]+ cores is reported. Binding strength and stereoselectivity have been correlated with the position of the amidinium group on the bipy. The 4-, 5- and 6-substituted ligands all produce C-[Re(CO)3(LH)Cl]X selectively, while only the 4-derivative gives preferred formation of Δ-[Ir(Phpy)2(4-LH)](BF4)2.

The Montreal Protocol protects the terrestrial carbon sink.

The control of the production of ozone-depleting substances through the Montreal Protocol means that the stratospheric ozone layer is recovering1 and that consequent increases in harmful surface ultraviolet radiation are being avoided2,3. The Montreal Protocol has co-benefits for climate change mitigation, because ozone-depleting substances are potent greenhouse gases4-7. The avoided ultraviolet radiation and climate change also have co-benefits for plants and their capacity to store carbon through photosynthesis8, but this has not previously been investigated. Here, using a modelling framework that couples ozone depletion, climate change, damage to plants by ultraviolet radiation and the carbon cycle, we explore the benefits of avoided increases in ultraviolet radiation and changes in climate on the terrestrial biosphere and its capacity as a carbon sink. Considering a range of strengths for the effect of ultraviolet radiation on plant growth8-12, we estimate that there could have been 325-690 billion tonnes less carbon held in plants and soils by the end of this century (2080-2099) without the Montreal Protocol (as compared to climate projections with controls on ozone-depleting substances). This change could have resulted in an additional 115-235 parts per million of atmospheric carbon dioxide, which might have led to additional warming of global-mean surface temperature by 0.50-1.0 degrees. Our findings suggest that the Montreal Protocol may also be helping to mitigate climate change through avoided decreases in the land carbon sink.

Reactions promoted by hypervalent iodine reagents and boron Lewis acids.

Understanding the role of boranes in hypervalent iodine chemistry will open up new reactivities which can be utilised in organic synthesis. Due to similar reactivities, λ3-iodanes have presented themselves as viable alternatives for many transformations dominated by transition metals whilst mitigating some of the associated drawbacks of metal systems. As showcased by recent reports, boranes can adopt a dual role in hypervalent iodine chemistry that surpasses mere activation of the hypervalent iodine reagent. Increased efforts to harness this potential with diverse boranes will uncover exciting reactivity with high applicability across various disciplines including adoption in the pharmaceutical sciences. This review will be relevant to the wider synthetic community including organic, inorganic, materials, and medicinal chemists due to the versatility of hypervalent iodine chemistry especially in combination with borane activation or participation. We aim to highlight the development of hypervalent iodine compounds including their structure, bonding, synthesis and utility in metal-free organic synthesis in combination with Lewis acidic boranes.

A review of quantum chemical studies of Frustrated Lewis Pairs.

This review endeavours to explore the power of quantum chemistry, especially density functional theory (DFT) to unravel mechanisms underlying the fascinating field of FLP chemistry. Apart from the fundamental mechanism of hydrogen activation by FLPs, borylation, silylation, polymerization, formation of heterocycles, reaction with small gaseous molecules, alkenes, terminal alkynes have also been reviewed. The role of DFT in understanding regio-selectivity, steric effects, London dispersion and covalent Interactions in FLPs are also discussed.

A hybrid bipy-NHC ligand for the construction of group 11 mixed-metal bimetallic complexes.

An asymmetric bipy/NHC ligand L has been used to construct Au/Au, Au/Ag and Au/Cu bimetallic complexes through prior coordination of the NHC to Au(i) and subsequent introduction of the second group 11 metal ion at the bipy donor of the hybrid ligand. The complex [Au(κC-L)2]BF4,1, has been used as the precursor for the formation of [AuAg(κ-C Au,κ2-N,N'Ag-1)2](BF4)2, 2a, [AuCu(κ-C Au,κ2-N,N'Cu-1)2](BF4)2, 2b and [AuAu'(κ-CAu/Au',κ1-NAu/Au'-1)2](BF4)2, 3.

Self-supervised learning for using overhead imagery as maps in outdoor range sensor localization.

Traditional approaches to outdoor vehicle localization assume a reliable, prior map is available, typically built using the same sensor suite as the on-board sensors used during localization. This work makes a different assumption. It assumes that an overhead image of the workspace is available and utilizes that as a map for use for range-based sensor localization by a vehicle. Here, range-based sensors are radars and lidars. Our motivation is simple, off-the-shelf, publicly available overhead imagery such as Google satellite images can be a ubiquitous, cheap, and powerful tool for vehicle localization when a usable prior sensor map is unavailable, inconvenient, or expensive. The challenge to be addressed is that overhead images are clearly not directly comparable to data from ground range sensors because of their starkly different modalities. We present a learned metric localization method that not only handles the modality difference, but is also cheap to train, learning in a self-supervised fashion without requiring metrically accurate ground truth. By evaluating across multiple real-world datasets, we demonstrate the robustness and versatility of our method for various sensor configurations in cross-modality localization, achieving localization errors on-par with a prior supervised approach while requiring no pixel-wise aligned ground truth for supervision at training. We pay particular attention to the use of millimeter-wave radar, which, owing to its complex interaction with the scene and its immunity to weather and lighting conditions, makes for a compelling and valuable use case.

kRadar++: Coarse-to-Fine FMCW Scanning Radar Localisation.

This paper presents a novel two-stage system which integrates topological localisation candidates from a radar-only place recognition system with precise pose estimation using spectral landmark-based techniques. We prove that the-recently available-seminal radar place recognition (RPR) and scan matching sub-systems are complementary in a style reminiscent of the mapping and localisation systems underpinning visual teach-and-repeat (VTR) systems which have been exhibited robustly in the last decade. Offline experiments are conducted on the most extensive radar-focused urban autonomy dataset available to the community with performance comparing favourably with and even rivalling alternative state-of-the-art radar localisation systems. Specifically, we show the long-term durability of the approach and of the sensing technology itself to autonomous navigation. We suggest a range of sensible methods of tuning the system, all of which are suitable for online operation. For both tuning regimes, we achieve, over the course of a month of localisation trials against a single static map, high recalls at high precision, and much reduced variance in erroneous metric pose estimation. As such, this work is a necessary first step towards a radar teach-and-repeat (RTR) system and the enablement of autonomy across extreme changes in appearance or inclement conditions.

Asymmetric ketone hydroboration catalyzed by alkali metal complexes derived from BINOL ligands.

The ability of alkali metal complexes featuring functionalized BINOL-derived ligands to catalyze ketone hydroboration reactions was explored. The reduced products were formed in excellent yields and with variable enantioselectivities dependent upon the nature of the ligand and the alkali metal cation.

Success of Montreal Protocol Demonstrated by Comparing High-Quality UV Measurements with "World Avoided" Calculations from Two Chemistry-Climate Models.

The Montreal Protocol on Substances that Deplete the Ozone Layer has been hailed as the most successful environmental treaty ever ( https://www.unenvironment.org/news-and-stories/story/montreal-protocol-triumph-treaty ). Yet, although our main concern about ozone depletion is the subsequent increase in harmful solar UV radiation at the Earth's surface, no studies to date have demonstrated its effectiveness in that regard. Here we use long-term UV Index (UVI) data derived from high-quality UV spectroradiometer measurements to demonstrate its success in curbing increases in UV radiation. Without this landmark agreement, UVI values would have increased at mid-latitude locations by approximately 20% between the early 1990s and today and would approximately quadruple at mid-latitudes by 2100. In contrast, an analysis of UVI data from multiple clean-air sites shows that maximum daily UVI values have remained essentially constant over the last ~20 years in all seasons, and may even have decreased slightly in the southern hemisphere, especially in Antarctica, where effects of ozone depletion were larger. Reconstructions of the UVI from total ozone data show evidence of increasing UVI levels in the 1980s, but unfortunately, there are no high-quality UV measurements available prior to the early 1990s to confirm these increases with direct observations.

Twisting the arm: structural constraints in bicyclic expanded-ring N-heterocyclic carbenes.

A series of diaryl, mono-aryl/alkyl and dialkyl mono- and bicyclic expanded-ring N-heterocyclic carbenes (ER-NHCs) have been prepared and their complexation to Au(i) investigated through the structural analysis of fifteen Au(NHC)X and/or [Au(NHC)2]X complexes. The substituted diaryl 7-NHCs are the most sterically encumbered with large buried volume (%VB) values of 40-50% with the less flexible six-membered analogues having %VB values at least 5% smaller. Although the bicyclic systems containing fused 6- and 7-membered rings (6,7-NHCs) are constrained with relatively acute NCN bond angles, they have the largest %VB values of the dialkyl derivatives reported here, a feature related to the fixed conformation of the heterocyclic rings and the compressional effect of a pre-set methyl substituent.

Halide and substituent dependent structural variation in copper(i) halide complexes of 1,5,9-triphosphacyclododecanes.

The reactions of 1,5,9-triethyl-1,5,9-triphosphacyclododecane, [12]-ane-P3Et3, and 1,5,9-tri(2-propyl)-1,5,9-triphosphacyclododecane, [12]-ane-P3iPr3 with copper(i)halides produce either bimetallic species of the type [([12]-ane-P3R3)Cu(CuX2)] (X = halide) or monomeric [([12]-ane-P3R3)CuX] depending on the nature of the halide and, to a lesser extent, the macrocycle. With CuCl only bimetallic complexes are formed with one copper centre bound to the macrocycle and a second attached through a Cu-Cu bond with a mono bridging chloride. CuBr affords monomeric [([12]-ane-P3R3)CuBr] complexes when performed in a 1 : 1 M : L ratio whereas the bimetallic compound [([12]-ane-P3Et3)(CuBr)2], resulted when a 2 : 1 ratio of M : L was employed. With CuI in all ratios only monomeric complexes were obtained. The synthesised complexes have been fully characterised by spectroscopic and analytical techniques and by determination of the molecular structures by single-crystal X-ray diffractometry.

Synthesis and photophysical properties of imine borane adducts towards vapochromic materials.

A series of alkynyl aryl conjugated aldehydes and imines were prepared and their adducts with various Lewis acidic boranes have been studied via NMR, absorption, and luminescence spectroscopies in solution. The imine-B(C6F5)3 adduct showed remarkable solution stability, and was then trialled in vapochromism experiments using simple impregnated paper strips to examine the fluorescence responses.

Asymmetric Cationic Phosphines: Synthesis, Coordination Chemistry, and Reactivity.

A single enantiomer of a cationic phosphine, [α-CgPAmHMe]BF4, containing two asymmetric subunits, an amidinium group (AmH) and a phosphacycle (CgP), has been synthesized and isolated. The ligand, which is of an extremely rare class, has been coordinated to Rh(I), Au(I), Ag(I), Cu(I), and Pt(0) to enable an empirical assessment of its donor properties. Analysis of the IR stretching frequency of the carbonyl ligand in trans-[Rh(α-CgPAmHMe)2(CO)Cl](BF4)2 coupled with metric data obtained from crystal-state molecular structures of pertinent complexes confirms the strong π-accepting properties of the ligand. The integrity of the N-P bond is compromised upon addition of base to both [Cu(α-CgPAmHMe)Cl]BF4 and [Ag(α-CgPAmHMe)(OTf)]BF4 where, instead of isolating anticipated chelating and/or bridging forms of the neutral, deprotonated α-CgPAmMe derivative, decomposition products were obtained containing a phosphacycle fragment and/or amidine ligands. The fragility of the N-P bond is also evident in uncoordinated [α-CgPAmHMe]BF4 as treatment with aqueous base releases a neutral amidine fragment and generates the P-P dimer [α,α-CgPP(O)Cg]. These fortuitous observations show [α-CgPAmHMe]BF4 to be a very useful synthon for the potential production of novel asymmetric phosphines.

Synthesis and characterisation of fluorescent aminophosphines and their coordination to gold(i).

Three novel fluorescent aminophosphine ligands have been synthesised that incorporate napthyl (L1), pyrenyl (L2) and anthraquinone (L3) chromophores into their structures. The ligands react with [AuCl(tht)] (tht = tetrahydrothiophene) to give neutral complexes of the form [AuCl(L1-3)]. Solid state, X-ray crystallographic data was obtained for the anthraquinone derivative, [AuCl(L3)], and showed a distorted linear coordination geometry at Au(i). The packing structure also revealed a number of intermolecular π-π interactions that involve the anthraquinone and phenyl units of the aminophosphine ligand. 31P NMR spectroscopic data revealed δP values of +42.2 (L1), +42.1 (L2) and +26.1 (L3) ppm, which shifted downfield upon coordination to Au(i) to +64.6, +64.7, and +55.8 ppm, respectively. Supporting TD-DFT studies were able to reproduce the structure and 31P NMR chemical shifts of [AuCl(L3)] as well as rationalise the HOMO-LUMO compositions. Photophysical studies showed that the appended fluorophore dominates the absorption and emission properties for the ligands and complexes, with the anthraquinone derivatives showing visible emission at ca. 570 nm which was attributed to the intramolecular charge transfer character of the phosphinoaminoanthraquinone fragment.

Ring-Expanded N-Heterocyclic Carbenes for Copper-Mediated Azide-Alkyne Click Cycloaddition Reactions.

A series of well-defined copper(I) complexes bearing ring-expanded N-heterocyclic carbene (NHC) ligands has been applied to the azide-alkyne cycloaddition reaction. The obtained results notably showed that the six-membered NHC ligands outperform well-established five-membered ones. [CuI(Mes-6)] displayed a remarkable catalytic activity while respecting the strict criteria for click reactions.