Continent-wide declines in shallow reef life over a decade of ocean warming.

Human society is dependent on nature1,2, but whether our ecological foundations are at risk remains unknown in the absence of systematic monitoring of species' populations3. Knowledge of species fluctuations is particularly inadequate in the marine realm4. Here we assess the population trends of 1,057 common shallow reef species from multiple phyla at 1,636 sites around Australia over the past decade. Most populations decreased over this period, including many tropical fishes, temperate invertebrates (particularly echinoderms) and southwestern Australian macroalgae, whereas coral populations remained relatively stable. Population declines typically followed heatwave years, when local water temperatures were more than 0.5 °C above temperatures in 2008. Following heatwaves5,6, species abundances generally tended to decline near warm range edges, and increase near cool range edges. More than 30% of shallow invertebrate species in cool latitudes exhibited high extinction risk, with rapidly declining populations trapped by deep ocean barriers, preventing poleward retreat as temperatures rise. Greater conservation effort is needed to safeguard temperate marine ecosystems, which are disproportionately threatened and include species with deep evolutionary roots. Fundamental among such efforts, and broader societal needs to efficiently adapt to interacting anthropogenic and natural pressures, is greatly expanded monitoring of species' population trends7,8.

Stabilisation of the [SiH6]2- Anion within a Supramolecular Assembly.

The hypercoordinate [SiH6]2- anion is not stable in solution. Here, we report the room temperature, solution stable molecular [SiH6]2- complex, [{KCa(NON)(OEt2)}2][SiH6] (NON=4,5-bis(2,6-diisopropylanilido)-2,7-di-tert-butyl-9,9-dimethyl-xanthene)), where the [SiH6]2- anion is stabilised within a supramolecular assembly that mimics the solid-state environment of the anion in the lattice of K2SiH6. Solution-state reactivity of the complex towards carbon monoxide, benzaldehyde, azobenzene and acetonitrile is reported, yielding a range of reduction and C-C coupled products.

Publisher Correction: Synthesis, structure and reaction chemistry of a nucleophilic aluminyl anion.

In Fig. 1 of this Letter, the hydrogen (H) atoms attached to each of the two nitrogen (N) atoms in the chemical structure of (NON)H2 were inadvertently missing. The original figure has been corrected online.

Synthesis, structure and reaction chemistry of a nucleophilic aluminyl anion.

The reactivity of aluminium compounds is dominated by their electron deficiency and consequent electrophilicity; these compounds are archetypal Lewis acids (electron-pair acceptors). The main industrial roles of aluminium, and classical methods of synthesizing aluminium-element bonds (for example, hydroalumination and metathesis), draw on the electron deficiency of species of the type AlR3 and AlCl31,2. Whereas aluminates, [AlR4]-, are well known, the idea of reversing polarity and using an aluminium reagent as the nucleophilic partner in bond-forming substitution reactions is unprecedented, owing to the fact that low-valent aluminium anions analogous to nitrogen-, carbon- and boron-centred reagents of the types [NX2]-, [CX3]- and [BX2]- are unknown3-5. Aluminium compounds in the +1 oxidation state are known, but are thermodynamically unstable with respect to disproportionation. Compounds of this type are typically oligomeric6-8, although monomeric systems that possess a metal-centred lone pair, such as Al(Nacnac)Dipp (where (Nacnac)Dipp = (NDippCR)2CH and R = t Bu, Me; Dipp = 2,6- i Pr2C6H3), have also been reported9,10. Coordination of these species, and also of (η5-C5Me5)Al, to a range of Lewis acids has been observed11-13, but their primary mode of reactivity involves facile oxidative addition to generate Al(III) species6-8,14-16. Here we report the synthesis, structure and reaction chemistry of an anionic aluminium(I) nucleophile, the dimethylxanthene-stabilized potassium aluminyl [K{Al(NON)}]2 (NON = 4,5-bis(2,6-diisopropylanilido)-2,7-di-tert-butyl-9,9-dimethylxanthene). This species displays unprecedented reactivity in the formation of aluminium-element covalent bonds and in the C-H oxidative addition of benzene, suggesting that it could find further use in both metal-carbon and metal-metal bond-forming reactions.

Inducing Nucleophilic Reactivity at Beryllium with an Aluminyl Ligand.

The reactions of anionic aluminium or gallium nucleophiles {K[E(NON)]}2 (E = Al, 1; Ga, 2; NON = 4,5-bis(2,6-diisopropylanilido)-2,7-ditert-butyl-9,9-dimethylxanthene) with beryllocene (BeCp2) led to the displacement of one cyclopentadienyl ligand at beryllium and the formation of compounds containing Be-Al or Be-Ga bonds (NON)EBeCp (E = Al, 3; Ga, 4). The Be-Al bond in the beryllium-aluminyl complex [2.310(4) Å] is much shorter than that found in the small number of previous examples [2.368(2) to 2.432(6) Å], and quantum chemical calculations suggest the existence of a non-nuclear attractor (NNA) for the Be-Al interaction. This represents the first example of a NNA for a heteroatomic interaction in an isolated molecular complex. As a result of this unusual electronic structure and the similarity in the Pauling electronegativities of beryllium and aluminium, the charge at the beryllium center (+1.39) in 3 is calculated to be less positive than that of the aluminium center (+1.88). This calculated charge distribution suggests the possibility for nucleophilic behavior at beryllium and correlates with the observed reactivity of the beryllium-aluminyl complex with N,N'-diisopropylcarbodiimide─the electrophilic carbon center of the carbodiimide undergoes nucleophilic attack by beryllium, thereby yielding a beryllium-diaminocarbene complex.

An Aluminium Imide as a Transfer Agent for the [NR]2- Function via Metathesis Chemistry.

The reactions of a terminal aluminium imide with a range of oxygen-containing substrates have been probed with a view to developing its use as a novel main group transfer agent for the [NR]2- fragment. We demonstrate transfer of the imide moiety to [N2 ], [CO] and [Ph(H)C] units driven thermodynamically by Al-O bond formation. N2 O reacts rapidly to generate the organoazide DippN3 (Dipp=2,6-i Pr2 C6 H3 ), while CO2 (under dilute reaction conditions) yields the corresponding isocyanate, DippNCO. Mechanistic studies, using both experimental and quantum chemical techniques, identify a carbamate complex K2 [(NON)Al-{κ2 -(N,O)-N(Dipp)CO2 }]2 (formed via [2+2] cycloaddition) as an intermediate in the formation of DippNCO, and also in an alternative reaction leading to the generation of the amino-dicarboxylate complex K2 [(NON)Al{κ2 -(O,O')-(O2 C)2 N-(Dipp)}] (via the take-up of a second equivalent of CO2 ). In the case of benzaldehyde, a similar [2+2] cycloaddition process generates the metallacyclic hemi-aminal complex, Kn [(NON)Al{κ2 -(N,O)-(N(Dipp)C(Ph)(H)O}]n . Extrusion of the imine, PhC(H)NDipp, via cyclo-reversion is disfavoured thermally, due to the high energy of the putative aluminium oxide co-product, K2 [(NON)Al(O)]2 . However, addition of CO2 allows the imine to be released, driven by the formation of the thermodynamically more stable aluminium carbonate co-product, K2 [(NON)Al(κ2 -(O,O')-CO3 )]2 .

Anionic Magnesium and Calcium Hydrides: Transforming CO into Unsaturated Disilyl Ethers.

The synthesis, characterisation and reactivity of two isostructural anionic magnesium and calcium complexes is reported. By X-ray and neutron diffraction techniques, the anionic hydrides are shown to exist as dimers, held together by a range of interactions between the two anions and two bridging potassium cations. Unlike the vast proportion of previously reported dimeric group 2 hydrides, which have hydrides that bridge two group 2 centres, here the hydrides are shown to be "terminal", but stabilised by interactions with the potassium cations. Both anionic hydrides were found to insert and couple CO under mild reaction conditions to give the corresponding group 2 cis-ethenediolate complexes. These cis-ethenediolate complexes were found to undergo salt elimination reactions with silyl chlorides, allowing access to small unsaturated disilyl ethers with a high percentage of their mass originating from the C1 source CO.

Coordination and Homologation of CO at Al(I): Mechanism and Chain Growth, Branching, Isomerization, and Reduction.

Homologation of carbon monoxide is central to the heterogeneous Fischer-Tropsch process for the production of hydrocarbon fuels. C-C bond formation has been modeled by homogeneous systems, with [CnOn]2- fragments (n = 2-6) formed by two-electron reduction being commonly encountered. Here, we show that four- or six-electron reduction of CO can be accomplished by the use of anionic aluminum(I) ("aluminyl") compounds to give both topologically linear and branched C4/C6 chains. We show that the mechanism for homologation relies on the highly electron-rich nature of the aluminyl reagent and on an unusual mode of interaction of the CO molecule, which behaves primarily as a Z-type ligand in initial adduct formation. The formation of [C6O6]4- from [C4O4]4- shows for the first time a solution-phase CO homologation process that brings about chain branching via complete C-O bond cleavage, while a comparison of the linear [C4O4]4- system with the [C4O4]6- congener formed under more reducing conditions models the net conversion of C-O bonds to C-C bonds in the presence of additional reductants.

Effects of human footprint and biophysical factors on the body-size structure of fished marine species.

Marine fisheries in coastal ecosystems in many areas of the world have historically removed large-bodied individuals, potentially impairing ecosystem functioning and the long-term sustainability of fish populations. Reporting on size-based indicators that link to food-web structure can contribute to ecosystem-based management, but the application of these indicators over large (cross-ecosystem) geographical scales has been limited to either fisheries-dependent catch data or diver-based methods restricted to shallow waters (<20 m) that can misrepresent the abundance of large-bodied fished species. We obtained data on the body-size structure of 82 recreationally or commercially targeted marine demersal teleosts from 2904 deployments of baited remote underwater stereo-video (stereo-BRUV). Sampling was at up to 50 m depth and covered approximately 10,000 km of the continental shelf of Australia. Seascape relief, water depth, and human gravity (i.e., a proxy of human impacts) were the strongest predictors of the probability of occurrence of large fishes and the abundance of fishes above the minimum legal size of capture. No-take marine reserves had a positive effect on the abundance of fishes above legal size, although the effect varied across species groups. In contrast, sublegal fishes were best predicted by gradients in sea surface temperature (mean and variance). In areas of low human impact, large fishes were about three times more likely to be encountered and fishes of legal size were approximately five times more abundant. For conspicuous species groups with contrasting habitat, environmental, and biogeographic affinities, abundance of legal-size fishes typically declined as human impact increased. Our large-scale quantitative analyses highlight the combined importance of seascape complexity, regions with low human footprint, and no-take marine reserves in protecting large-bodied fishes across a broad range of species and ecosystem configurations.

Las pesquerías marinas de los ecosistemas costeros en muchas áreas del mundo históricamente han removido a individuos de gran tamaño, potencialmente perjudicando el funcionamiento ambiental y la sostenibilidad a largo plazo de las poblaciones de peces. Los reportes sobre los indicadores basados en el tamaño que se vinculan con la estructura de la red alimenticia pueden contribuir al manejo basado en el ecosistema, aunque la aplicación de estos indicadores a grandes (inter-ecosistemas) escalas geográficas ha estado limitada a datos de captura dependientes de las pesquerías o métodos basados en el buceo restringidos a aguas someras (<20 m), lo cual puede representar erróneamente la abundancia de peces de gran tamaño capturados para la pesca. Obtuvimos los datos de la estructura del tamaño corporal de 82 teleósteos marinos demersales focalizados por razones recreativas o comerciales tomados de 2,904 despliegues de video estéreo subacuático remoto con cebo (stereo-BRUV, en inglés). El muestreo se realizó hasta los 50 metros de profundidad y abarcó aproximadamente 10,000 km del talud continental de Australia. El relieve marino, la profundidad del agua y la gravedad humana (es decir, un indicador de los impactos humanos) fueron los pronosticadores más sólidos de la probabilidad de incidencia de los peces de gran tamaño y de la abundancia de peces por encima del tamaño legal mínimo de captura. Las reservas marinas de protección total tienen un efecto positivo sobre la abundancia de los peces que están por encima del tamaño legal, aunque el efecto varió según el grupo de especies. Como contraste, los peces de tamaño sublegal fueron pronosticados de mejor manera usando gradientes de la temperatura de la superficie marina (media y varianza). En las áreas con un impacto humano reducido, los peces de gran tamaño corporal tenían hasta tres veces mayor probabilidad de aparecer y los peces de tamaño legal eran aproximadamente cinco veces más abundantes. Para los grupos de especies conspicuas con afinidades contrastantes de hábitat, ambiente y biogeografía, la abundancia de peces de tamaño legal normalmente declinó conforme aumentó el impacto humano. Nuestros análisis cuantitativos a gran escala resaltan la importancia conjunta que tienen la complejidad marina, las regiones con una huella humana reducida y las reservas marinas de protección total para la protección de los peces de gran tamaño corporal en una extensa gama de especies y configuraciones ecosistémicas. Efectos de la Huella Humana y los Factores Biofísicos sobre la Estructura del Tamaño Corporal de Especies Marinas Capturadas para la Pesca.

Crystalline Germanium(I) and Tin(I) Centered Radical Anions.

An isostructural series of heavy Group 14 E(I) radical anions (Ge, Sn, Pb), stabilized by a bulky xanthene-based diamido ligand are reported. The radical anions were synthesised by the one-electron reduction of their corresponding E(II) precursor complexes with sodium naphthalenide in THF, yielding the radical anions as charge-separated sodium salts. The series of main group radicals have been comprehensively characterized by EPR spectroscopy, X-ray crystallography and DFT analysis, which reveal that in all cases, the spin density of the unpaired electron almost exclusively resides in a p-orbital of π symmetry located on the Group 14 center.

Controlling Oxidative Addition and Reductive Elimination at Tin(I) via Hemi-Lability.

We report on the synthesis of a distannyne supported by a pincer ligand bearing pendant amine donors that is capable of reversibly activating E-H bonds at one or both of the tin centres through dissociation of the hemi-labile N-Sn donor/acceptor interactions. This chemistry can be exploited to sequentially (and reversibly) assemble mixed-valence chains of tin atoms of the type ArSn{Sn(Ar)H}n SnAr (n=1, 2). The experimentally observed (decreasing) propensity towards chain growth with increasing chain length can be rationalized both thermodynamically and kinetically by the electron- withdrawing properties of the -Sn(Ar)H- backbone units generated via oxidative addition.

Partnering a Three-Coordinate Gallium Cation with a Hydroborate Counter-Ion for the Catalytic Hydrosilylation of CO2.

A novel ß-diketiminate stabilized gallium hydride, (Dipp L)Ga(Ad)H (where (Dipp L)={HC(MeCDippN)2 }, Dipp=2,6-diisopropylphenyl and Ad=1-adamantyl), has been synthesized and shown to undergo insertion of carbon dioxide into the Ga-H bond under mild conditions. In this case, treatment of the resulting κ1 -formate complex with triethylsilane does not lead to regeneration of the hydride precursor. However, when combined with B(C6 F5 )3 , (Dipp L)Ga(Ad)H catalyses the reductive hydrosilylation of CO2 . Under stoichiometric conditions, the addition of one equivalent of B(C6 F5 )3 to (Dipp L)Ga(Ad)H leads to the formation of a 3-coordinate cationic gallane complex, partnered with a hydroborate anion, [(Dipp L)Ga(Ad)][HB(C6 F5 )3 ]. This complex rapidly hydrometallates carbon dioxide and catalyses the selective reduction of CO2 to the formaldehyde oxidation level at 60 °C in the presence of Et3 SiH (yielding H2 C(OSiEt3 )2 ). When catalysis is undertaken in the presence of excess B(C6 F5 )3 , appreciable enhancement of activity is observed, with a corresponding reduction in selectivity: the product distribution includes H2 C(OSiEt3 )2 , CH4 and O(SiEt3 )2 . While this system represents proof-of-concept in CO2 hydrosilylation by a gallium hydride system, the TOF values obtained are relatively modest (max. 10 h-1 ). This is attributed to the strength of binding of the formatoborate anion to the gallium centre in the catalytic intermediate (Dipp L)Ga(Ad){OC(H)OB(C6 F5 )3 }, and the correspondingly slow rate of the turnover-limiting hydrosilylation step. In turn, this strength of binding can be related to the relatively high Lewis acidity measured for the [(Dipp L)Ga(Ad)]+ cation (AN=69.8).

The Aluminyl Anion: A New Generation of Aluminium Nucleophile.

Trivalent aluminium compounds are well known for their reactivity as Lewis acids/electrophiles, a feature that is exploited in many pharmaceutical, industrial and laboratory-based reactions. Recently, a series of isolable aluminium(I) anions ("aluminyls") have been reported, which offer an alternative to this textbook description: these reagents behave as aluminium nucleophiles. This minireview covers the synthesis, structure and reactivity of aluminyl species reported to date, together with their associated metal complexes. The frontier orbitals of each of these species have been investigated using a common methodology to allow for a like-for-like comparison of their electronic structure and a means of rationalising (sometimes unprecedented) patterns of reactivity.

Approaching a "Naked" Boryl Anion: Amide Metathesis as a Route to Calcium, Strontium, and Potassium Boryl Complexes.

Amide metathesis has been used to generate the first structurally characterized boryl complexes of calcium and strontium, {(Me3 Si)2 N}M{B(NDippCH)2 }(thf)n (M=Ca, n=2; M=Sr, n=3), through the reactions of the corresponding bis(amides), M{N(SiMe3 )2 }2 (thf)2 , with (thf)2 Li- {B(NDippCH)2 }. Most notably, this approach can also be applied to the analogous potassium amide K{N(SiMe3 )2 }, leading to the formation of the solvent-free borylpotassium dimer [K{B(NDippCH)2 }]2 , which is stable in the solid state at room temperature for extended periods (48 h). A dimeric structure has been determined crystallographically in which the K+ cations interact weakly with both the ipso-carbons of the flanking Dipp groups and the boron centres of the diazaborolyl heterocycles, with K⋅⋅⋅B distances of >3.1 Å. These structural features, together with atoms in molecules (QTAIM) calculations imply that the boron-containing fragment closely approaches a limiting description as a "free" boryl anion in the condensed phase.

Probing the Extremes of Covalency in M-Al bonds: Lithium and Zinc Aluminyl Compounds.

Synthetic routes to lithium, magnesium, and zinc aluminyl complexes are reported, allowing for the first structural characterization of an unsupported lithium-aluminium bond. Crystallographic and quantum-chemical studies are consistent with the presence of a highly polar Li-Al interaction, characterized by a low bond order and relatively little charge transfer from Al to Li. Comparison with magnesium and zinc aluminyl systems reveals changes to both the M-Al bond and the (NON)Al fragment (where NON=4,5-bis(2,6-diisopropylanilido)-2,7-di-tert-butyl-9,9-dimethylxanthene), consistent with a more covalent character, with the latter complex being shown to react with CO2 via a pathway that implies that the zinc centre acts as the nucleophilic partner.

Activation of Protic, Hydridic and Apolar E-H Bonds by a Boryl-Substituted GeII Cation.

The synthesis of a boryl-substituted germanium(II) cation, [Ge{B(NDippCH)2 }(IPrMe)]+ , (Dipp=2,6-diisopropylphenyl) featuring a supporting N-heterocyclic carbene (NHC) donor, has been explored through chloride abstraction from the corresponding (boryl)(NHC)GeCl precursor. Crystallographic studies in the solid state and UV/Vis spectra in fluorobenzene solution show that this species dimerizes under such conditions to give [(IPrMe){(HCNDipp)2 B}Ge=Ge{B(NDippCH)2 }(IPrMe)]2+ (IPrMe = 1,3-diisopropyl-4,5-dimethylimidazolin-2-ylidene), which can be viewed as an imidazolium-functionalized digermene. The dimer is cleaved in the presence of donor solvents such as [D8 ]thf or [D5 ]pyridine, to give monomeric adducts of the type [Ge{B(NDippCH)2 }(IPrMe)(L)]+ . In the case of the thf adduct, the additional donor is shown to be sufficiently labile that it can act as a convenient in situ source of the monomeric complex [Ge{B(NDippCH)2 }(IPrMe)]+ for oxidative bond-activation chemistry. Thus, [Ge{B(NDippCH)2 }(IPrMe)(thf)]+ reacts with silanes and dihydrogen, leading to the formation of GeIV products, whereas the cleavage of the N-H bond in ammonia ultimately yields products containing C-H and B-N bonds. The facile reactivity observed in E-H bond activation is in line with the very small calculated HOMO-LUMO gap (132 kJ mol-1 ).

Arene C-H Activation at Aluminium(I): meta Selectivity Driven by the Electronics of SN Ar Chemistry.

The reactivity of the electron-rich anionic AlI aluminyl compound K2 [(NON)Al]2 (NON=4,5-bis(2,6-diisopropylanilido)-2,7-di-tert-butyl-9,9-dimethylxanthene) towards mono- and disubstituted arenes is reported. C-H activation chemistry with n-butylbenzene gives exclusively the product of activation at the arene meta position. Mechanistically, this transformation proceeds in a single step via a concerted Meisenheimer-type transition state. Selectivity is therefore based on similar electronic factors to classical SN Ar chemistry, which implies the destabilisation of transition states featuring electron-donating groups in either ortho or para positions. In the cases of toluene and the three isomers of xylene, benzylic C-H activation is also possible, with the product(s) formed reflecting the feasibility (or otherwise) of competing arene C-H activation at a site which is neither ortho nor para to a methyl substituent.

Carbon Monoxide Activation by a Molecular Aluminium Imide: C-O Bond Cleavage and C-C Bond Formation.

Anionic molecular imide complexes of aluminium are accessible via a rational synthetic approach involving the reactions of organo azides with a potassium aluminyl reagent. In the case of K2 [(NON)Al(NDipp)]2 (NON=4,5-bis(2,6-diisopropylanilido)-2,7-di-tert-butyl-9,9-dimethyl-xanthene; Dipp=2,6-diisopropylphenyl) structural characterization by X-ray crystallography reveals a short Al-N distance, which is thought primarily to be due to the low coordinate nature of the nitrogen centre. The Al-N unit is highly polar, and capable of the activation of relatively inert chemical bonds, such as those found in dihydrogen and carbon monoxide. In the case of CO, uptake of two molecules of the substrate leads to C-C coupling and C≡O bond cleavage. Thermodynamically, this is driven, at least in part, by Al-O bond formation. Mechanistically, a combination of quantum chemical and experimental observations suggests that the reaction proceeds via exchange of the NR and O substituents through intermediates featuring an aluminium-bound isocyanate fragment.

Reversible, Room-Temperature C-C Bond Activation of Benzene by an Isolable Metal Complex.

The activation of C-C bonds is of fundamental interest in the construction of complex molecules from petrochemical feedstocks. In the case of the archetypal aromatic hydrocarbon benzene, C-C cleavage is thermodynamically disfavored, and is brought about only by transient highly reactive species generated in situ. Here we show that the oxidative addition of the C-C bond in benzene by an isolated metal complex is not only possible, but occurs at room temperature and reversibly at a single aluminium center in [(NON)Al]- (where NON = 4,5-bis(2,6-diisopropylanilido)-2,7-di-tert-butyl-9,9-dimethylxanthene). Selectivity over C-H bond activation is achieved kinetically and allows for the generation of functionalized acyclic products from benzene.

An Acid-Free Anionic Oxoborane Isoelectronic with Carbonyl: Facile Access and Transfer of a Terminal B═O Double Bond.

We disclose the synthesis and structural characterization of the first acid-free anionic oxoborane, [K(2.2.2-crypt)][(HCDippN)2BO] (1) (Dipp = 2,6- iPr2C6H3), which is isoelectronic with classical carbonyl compounds. 1 can readily be accessed from its borinic acid by a simple deprotonation/sequestration sequence. Crystallographic and density functional theory (DFT) analyses support the presence of a polarized terminal B═O double bond. Subsequent π bond metathesis converts the B═O bond to a heavier B═S containing system, affording the first anionic thioxoborane [K(2.2.2-crypt)][(HCDippN)2BS] (2), isoelectronic with thiocarbonyls. Facile B═O bond cleavage can also be achieved to access B-H and B-Cl bonds and, via a remarkable oxide (O2-) ion abstraction, to generate a borenium cation [(HCDippN)2B(NC5H5)][OTf] (4). By extension, 1 can act as an oxide transfer agent to organic substrates, a synthetic role traditionally associated with transition-metal compounds. Hence we show that B-O linkages, which are often considered to be thermodynamic sinks, can be activated under mild conditions toward bond cleavage and transfer, by exploiting the higher reactivity inherent in the B═O double bond.