TMEDA in Iron‐Catalyzed Hydromagnesiation: Formation of Iron(II)‐Alkyl Species for Controlled Reduction to Alkene‐Stabilized Iron(0)

N,N,N’,N’‐Tetramethylethylenediamine (TMEDA) has been one of the most prevalent and successful additives used in iron‐catalysis, finding application in reactions as diverse as cross‐coupling, C‐H activation and borylation. However, the role that TMEDA plays in these reactions remains largely undefined. Herein, studying the iron‐catalyzed hydromagnesiation of styrene derivatives using TMEDA has provided molecular‐level insight into the role of TMEDA in achieving effective catalysis. Key is the initial formation of TMEDA‐iron(II) alkyl species which undergo a controlled reduction to selectively form catalytically active styrene‐stabilized iron(0)‐alkyl complexes. While TMEDA is not bound to the catalytically active species, these active iron(0) complexes cannot be accessed in the absence of TMEDA. This mode of action, allowing for controlled reduction and access to iron(0) species, represents a new paradigm for the role of this important reaction additive in iron catalysis

Hyper-compressions: The rise of flash fiction in “post-transitional” South Africa

Blair, P. (2020). Hyper-compressions: The rise of flash fiction in “post-transitional” South Africa', The Journal of Commonwealth Literature, 55(1), 38-60. Copyright © 2018. Reprinted by permission of SAGE Publications.This article begins with a survey of flash fiction in “post-transitional” South Africa, which it relates to the nation’s post-apartheid canon of short stories and short-short stories, to the international rise of flash fiction and “sudden fiction”, and to the historical particularities of South Africa’s “post-transition”. It then undertakes close readings of three flash fictions republished in the article, each less than 450 words: Tony Eprile’s “The interpreter for the tribunal” (2007), which evokes the psychological and ethical complexities, and long-term ramifications, of the Truth and Reconciliation Commission; Michael Cawood Green’s “Music for a new society” (2008), a carjacking story that invokes discourses about violent crime and the “‘new’ South Africa”; and Stacy Hardy’s “Kisula” (2015), which maps the psychogeography of cross-racial sex and transnational identity-formation in an evolving urban environment. The article argues that these exemplary flashes are “hyper-compressions”, in that they compress and develop complex themes with a long literary history and a wide contemporary currency. It therefore contends that flash fiction of South Africa’s post-transition should be recognized as having literary-historical significance, not just as an inherently metonymic form that reflects, and alludes to, a broader literary culture, but as a genre in its own right

AVONET: morphological, ecological and geographical data for all birds

Functional traits offer a rich quantitative framework for developing and testing theories in evolutionary biology, ecology and ecosystem science. However, the potential of functional traits to drive theoretical advances and refine models of global change can only be fully realised when species‐level information is complete. Here we present the AVONET dataset containing comprehensive functional trait data for all birds, including six ecological variables, 11 continuous morphological traits, and information on range size and location. Raw morphological measurements are presented from 90,020 individuals of 11,009 extant bird species sampled from 181 countries. These data are also summarised as species averages in three taxonomic formats, allowing integration with a global phylogeny, geographical range maps, IUCN Red List data and the eBird citizen science database. The AVONET dataset provides the most detailed picture of continuous trait variation for any major radiation of organisms, offering a global template for testing hypotheses and exploring the evolutionary origins, structure and functioning of biodiversity

Mechanism of the bis(imino)pyridine-iron-catalyzed hydromagnesiation of styrene derivatives

Iron-catalyzed hydromagnesiation of styrene derivatives offers a rapid and efficient method to generate benzylic Grignard reagents, which can be applied in a range of transformations to provide products of formal hydrofunctionalization. While iron-catalyzed methodologies exist for the hydromagnesiation of terminal alkenes, internal alkynes, and styrene derivatives, the underlying mechanisms of catalysis remain largely undefined. To address this issue and determine the divergent reactivity from established cross-coupling and hydrofunctionalization reactions, a detailed study of the bis(imino)pyridine iron-catalyzed hydromagnesiation of styrene derivatives is reported. Using a combination of kinetic analysis, deuterium labeling, and reactivity studies as well as in situ Fe Mössbauer spectroscopy, key mechanistic features and species were established. A formally iron(0) ate complex [ BIPFe(Et)(CH═CH)] was identified as the principle resting state of the catalyst. Dissociation of ethene forms the catalytically active species which can reversibly coordinate the styrene derivative and mediate a direct and reversible β-hydride transfer, negating the necessity of a discrete iron hydride intermediate. Finally, displacement of the tridentate bis(imino)pyridine ligand over the course of the reaction results in the formation of a tris-styrene-coordinated iron(0) complex, which is also a competent catalyst for hydromagnesiation

Activation of ammonia and hydrazine by electron rich Fe(ii) complexes supported by a dianionic pentadentate ligand platform through a common terminal Fe(iii) amido intermediate

International audienceWe report the use of electron rich iron complexes supported by a dianionic diborate pentadentate ligand system, B(2)Pz(4)Py, for the coordination and activation of ammonia (NH3) and hydrazine (NH2NH2). For ammonia, coordination to neutral (B(2)Pz(4)Py)Fe(ii) or cationic [(B(2)Pz(4)Py)Fe(iii)](+) platforms leads to well characterized ammine complexes from which hydrogen atoms or protons can be removed to generate, fleetingly, a proposed (B(2)Pz(4)Py)Fe(iii)-NH2 complex (3(Ar)-NH2). DFT computations suggest a high degree of spin density on the amido ligand, giving it significant aminyl radical character. It rapidly traps the H atom abstracting agent 2,4,6-tri-tert-butylphenoxy radical (ArO) to form a C-N bond in a fully characterized product (2(Ar)), or scavenges hydrogen atoms to return to the ammonia complex (B(2)Pz(4)Py)Fe(ii)-NH3 (1(Ar)-NH3). Interestingly, when (B(2)Pz(4)Py)Fe(ii) is reacted with NH2NH2, a hydrazine bridged dimer, (B(2)Pz(4)Py)Fe(ii)-NH2NH2-Fe(ii)(B(2)Pz(4)Py) ((1(Ar))(2)-NH2NH2), is observed at -78 degrees C and converts to a fully characterized bridging diazene complex, 4(Ar), along with ammonia adduct 1(Ar)-NH3 as it is allowed to warm to room temperature. Experimental and computational evidence is presented to suggest that (B(2)Pz(4)Py)Fe(ii) induces reductive cleavage of the N-N bond in hydrazine to produce the Fe(iii)-NH2 complex 3(Ar)-NH2, which abstracts H atoms from (1(Ar))(2)-NH2NH2 to generate the observed products. All of these transformations are relevant to proposed steps in the ammonia oxidation reaction, an important process for the use of nitrogen-based fuels enabled by abundant first row transition metals

Avonet : morphological, ecological and geographical data for all birds

Functional traits offer a rich quantitative framework for developing and testing theories in evolutionary biology, ecology and ecosystem science. However, the potential of functional traits to drive theoretical advances and refine models of global change can only be fully realised when species-level information is complete. Here we present the AVONET dataset containing comprehensive functional trait data for all birds, including six ecological variables, 11 continuous morphological traits, and information on range size and location. Raw morphological measurements are presented from 90,020 individuals of 11,009 extant bird species sampled from 181 countries. These data are also summarised as species averages in three taxonomic formats, allowing integration with a global phylogeny, geographical range maps, IUCN Red List data and the eBird citizen science database. The AVONET dataset provides the most detailed picture of continuous trait variation for any major radiation of organisms, offering a global template for testing hypotheses and exploring the evolutionary origins, structure and functioning of biodiversity.Peer reviewe