Contreras Leslie (chequeslash5)

Most functional groups, especially those consisting of the abundant elements of organic matter-carbon, nitrogen and oxygen-have been extensively studied and only very few remain speculative due to their high intrinsic reactivity. In contrast to the well-explored chemistry of diazoalkanes (R2C=N2), diazoalkenes (R2C=C=N2) have been postulated in several organic transformations, but remain elusive long-sought intermediates. Here, we present a room-temperature stable diazoalkene, utilizing a dinitrogen transfer from nitrous oxide. This functional group shows dual-site nucleophilicity (C and N atoms) and features a bent C-C-N entity (124°) and a long N-N bond together with a remarkable low infrared absorption (1,944 cm-1). Substitution of N2 by an isocyanide leads to a vinylidene ketenimine. Furthermore, photochemically triggered loss of dinitrogen might proceed through a transient triplet vinylidene. We anticipate the existence of a stable diazoalkene functional group to pave an exciting avenue into the chemistry of low-valent carbon and unsaturated carbenes.A Correction to this paper has been published https//doi.org/10.1038/s41556-021-00686-x.A Correction to this paper has been published https//doi.org/10.1038/s41556-021-00687-w.Animals and plants are shifting the timing of key life events in response to climate change, yet despite recent documentation of escalating phenological change, scientists lack a full understanding of how and why phenological responses vary across space and among species. Here, we used over 7 million community-contributed bird observations to derive species-specific, spatially explicit estimates of annual spring migration phenology for 56 bird species across eastern North America. We show that changes in the spring arrival of migratory birds are coarsely synchronized with fluctuations in vegetation green-up and that the sensitivity of birds to plant phenology varied extensively. Bird arrival responded more synchronously with vegetation green-up at higher latitudes, where phenological shifts over time are also greater. Critically, species' migratory traits explained variation in sensitivity to green-up, with species that migrate more slowly, arrive earlier and overwinter further north showing greater responsiveness to earlier springs. Identifying how and why species vary in their ability to shift phenological events is fundamental to predicting species' vulnerability to climate change. Such variation in sensitivity across taxa, with long-distance neotropical migrants exhibiting reduced synchrony, may help to explain substantial declines in these species over the last several decades.Tropical cloud forests (TCFs) are one of the world's most species- and endemism-rich terrestrial ecosystems. TCFs are threatened by direct human pressures and climate change, yet the fate of these extraordinary ecosystems remains insufficiently quantified. With discussions of the post-2020 biodiversity framework underway, TCFs are a defining test case of the success and promise of recent policy targets and their associated mechanisms to avert the global biodiversity crisis. Here we present a global assessment of the recent status and trends of TCFs and their biodiversity and evaluate the efficacy of current protection measures. We find that cloud forests occupied 0.4% of the global land surface in 2001 and harboured ~3,700 species of birds, mammal, amphibians and tree ferns (~15% of the global diversity of those groups), with half of those species entirely restricted to cloud forests. Worldwide, ~2.4% of cloud forests (in some regions, more than 8%) were lost between 2001 and 2018, especially in readily accessible places. While protected areas have slowed this decline, a large proportion of loss in TCF cover is still occurring despite formal protection. click here Increased conservation efforts are needed to avert the impending regional or global demise of TCFs and their unique biodiversity.This Review focuses on the mech