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The importance of phosphorus (P) in regulating ecosystem responses to climate change has fostered P-cycle implementation in land surface models, but their CO₂effects predictions have not been evaluated against measurements. Here, we perform a data-driven model evaluation where simulations of eight widely used P-enabled models were confronted with observations from a long-term free-air CO₂enrichment experiment in a mature, P-limitedEucalyptusforest. We show that most models predicted the correct sign and magnitude of the CO₂effect on ecosystem carbon (C) sequestration, but they generally overestimated the effects on plant C uptake and growth. We identify leaf-to-canopy scaling of photosynthesis, plant tissue stoichiometry, plant belowground C allocation, and the subsequent consequences for plant-microbial interaction as key areas in which models of ecosystem C-P interaction can be improved. Together, this data-model intercomparison reveals data-driven insights into the performance and functionality of P-enabled models and adds to the existing evidence that the global CO₂-driven carbon sink is overestimated by models. 

Forest ecosystems are important global soil carbon (C) reservoirs, but their capacity to sequester C is susceptible to climate change factors that alter the quantity and quality of C inputs. To better understand forest soil C responses to altered C inputs, we integrated three molecular composition published data sets of soil organic matter (SOM) and soil microbial communities for mineral soils after 20 years of detrital input and removal treatments in two deciduous forests: Bousson Forest (BF), Harvard Forest (HF), and a coniferous forest: H.J. Andrews Forest (HJA). Soil C turnover times were estimated from radiocarbon measurements and compared with the molecular‐level data (based on nuclear magnetic resonance and specific analysis of plant‐ and microbial‐derived compounds) to better understand how ecosystem properties control soil C biogeochemistry and dynamics. Doubled aboveground litter additions did not increase soil C for any of the forests studied likely due to long‐term soil priming. The degree of SOM decomposition was higher for bacteria‐dominated sites with higher nitrogen (N) availability while lower for the N‐poor coniferous forest. Litter exclusions significantly decreased soil C, increased SOM decomposition state, and led to the adaptation of the microbial communities to changes in available substrates. Finally, although aboveground litter determined soil C dynamics and its molecular composition in the coniferous forest (HJA), belowground litter appeared to be more influential in broadleaf deciduous forests (BH and HF). This synthesis demonstrates that inherent ecosystem properties regulate how soil C dynamics change with litter manipulations at the molecular‐level. Across the forests studied, 20 years of litter additions did not enhance soil C content, whereas litter reductions negatively impacted soil C concentrations. These results indicate that soil C biogeochemistry at these temperate forests is highly sensitive to changes in litter deposition, which are a product of environmental change drivers. 

Nickel complexes have been widely employed as catalysts in C–C and C–heteroatom bond formation reactions. While Ni(0), Ni( i ), and Ni( ii ) intermediates are most relevant in these transformations, recently Ni( iii ) and Ni( iv ) species have also been proposed to play a role in catalysis. Reported herein is the synthesis, detailed characterization, and reactivity of a series of Ni( ii ) and Ni( iii ) metallacycle complexes stabilized by tetradentate pyridinophane ligands with various N-substituents. Interestingly, while the oxidation of the Ni( ii ) complexes with various other oxidants led to exclusive C–C bond formation in very good yields, the use of O 2 or H 2 O 2 as oxidants led to formation of appreciable amounts of C–O bond formation products, especially for the Ni( ii ) complex supported by an asymmetric pyridinophane ligand containing one tosyl N-substituent. Moreover, cryo-ESI-MS studies support the formation of several high-valent Ni species as key intermediates in this uncommon Ni-mediated oxygenase-type chemistry. 

ABSTRACT G0.253+0.016, aka ‘the Brick’, is one of the most massive (>105 M⊙) and dense (>104 cm−3) molecular clouds in the Milky Way’s Central Molecular Zone. Previous observations have detected tentative signs of active star formation, most notably a water maser that is associated with a dust continuum source. We present ALMA Band 6 observations with an angular resolution of 0.13 arcsec (1000 AU) towards this ‘maser core’ and report unambiguous evidence of active star formation within G0.253+0.016. We detect a population of eighteen continuum sources (median mass ∼2 M⊙), nine of which are driving bi-polar molecular outflows as seen via SiO (5–4) emission. At the location of the water maser, we find evidence for a protostellar binary/multiple with multidirectional outflow emission. Despite the high density of G0.253+0.016, we find no evidence for high-mass protostars in our ALMA field. The observed sources are instead consistent with a cluster of low-to-intermediate-mass protostars. However, the measured outflow properties are consistent with those expected for intermediate-to-high-mass star formation. We conclude that the sources are young and rapidly accreting, and may potentially form intermediate- and high-mass stars in the future. The masses and projected spatial distribution of the cores are generally consistent with thermal fragmentation, suggesting that the large-scale turbulence and strong magnetic field in the cloud do not dominate on these scales, and that star formation on the scale of individual protostars is similar to that in Galactic disc environments. 

High valent iron species are very reactive molecules involved in oxidation reactions of relevance to biology and chemical synthesis. Herein we describe iron( iv )–tosylimido complexes [Fe IV (NTs)(MePy 2 tacn)](OTf) 2 ( 1(IV)NTs ) and [Fe IV (NTs)(Me 2 (CHPy 2 )tacn)](OTf) 2 ( 2(IV)NTs ), (MePy 2 tacn = N -methyl- N , N -bis(2-picolyl)-1,4,7-triazacyclononane, and Me 2 (CHPy 2 )tacn = 1-(di(2-pyridyl)methyl)-4,7-dimethyl-1,4,7-triazacyclononane, Ts = Tosyl). 1(IV)NTs and 2(IV)NTs are rare examples of octahedral iron( iv )–imido complexes and are isoelectronic analogues of the recently described iron( iv )–oxo complexes [Fe IV (O)(L)] 2+ (L = MePy 2 tacn and Me 2 (CHPy 2 )tacn, respectively). 1(IV)NTs and 2(IV)NTs are metastable and have been spectroscopically characterized by HR-MS, UV-vis, 1 H-NMR, resonance Raman, Mössbauer, and X-ray absorption (XAS) spectroscopy as well as by DFT computational methods. Ferric complexes [Fe III (HNTs)(L)] 2+ , 1(III)–NHTs (L = MePy 2 tacn) and 2(III)–NHTs (L = Me 2 (CHPy 2 )tacn) have been isolated after the decay of 1(IV)NTs and 2(IV)NTs in solution, spectroscopically characterized, and the molecular structure of [Fe III (HNTs)(MePy 2 tacn)](SbF 6 ) 2 determined by single crystal X-ray diffraction. Reaction of 1(IV)NTs and 2(IV)NTs with different p -substituted thioanisoles results in the transfer of the tosylimido moiety to the sulphur atom producing sulfilimine products. In these reactions, 1(IV)NTs and 2(IV)NTs behave as single electron oxidants and Hammett analyses of reaction rates evidence that tosylimido transfer is more sensitive than oxo transfer to charge effects. In addition, reaction of 1(IV)NTs and 2(IV)NTs with hydrocarbons containing weak C–H bonds results in the formation of 1(III)–NHTs and 2(III)–NHTs respectively, along with the oxidized substrate. Kinetic analyses indicate that reactions proceed via a mechanistically unusual HAT reaction, where an association complex precedes hydrogen abstraction.