Unexpected Nickel Complex Speciation Unlocks Alternative Pathways for the Reactions of Alkyl Halides with dppf-Nickel(0)

The mechanism of the reactions between dppf-Ni0 complexes and alkyl halides has been investigated using kinetic and mechanistic experiments and DFT calculations. The active species is [Ni(κ2-dppf)(κ1-dppf)], which undergoes a halide abstraction reaction with alkyl halides and rapidly captures the alkyl radical that is formed. The rates of the reactions of [Ni(COD)(dppf)] with alkyl halides and the yields of prototypical nickel-catalyzed Kumada cross-coupling reactions of alkyl halides are shown to be significantly improved by the addition of free dppf ligand

{N,N′-[2,2′-(Ethane-1,2-diyldisulfanediyl)di-o-phenyl­ene]bis­(quinoline-2-carboxamidato)}copper(II)

In the title compound, [Cu(C34H24N4O2S2)] or [Cu(bqdapte)], where H2bqdapte is 1,2-{bis­[2-(quinoline-2-carboxamido)­phen­yl]sulfan­yl}ethane, the CuII ion is coordinated to the dianionic hexa­dentate bqdapte2− ligand by two amide and two quinoline N atoms and two thio­ether S atoms. In the observed conformation of the hexa­dentate ligand, the quinoline rings attain positions related by a twofold axis. The Cu atom displays a Jahn–Teller-distorted octa­hedral CuN4S2 geometry axially compressed along the two trans-configured Cu—Namidate bonds

High-Quality draft genome sequence of the Lotus spp. microsymbiont Mesorhizobium loti strain CJ3Sym

Mesorhizobium loti strain CJ3Sym was isolated in 1998 following transfer of the integrative and conjugative element ICEMlSymR7A, also known as the R7A symbiosis island, in a laboratory mating from the donor M. loti strain R7A to a nonsymbiotic recipient Mesorhizobium strain CJ3. Strain CJ3 was originally isolated from a field site in the Rocklands range in New Zealand in 1994. CJ3Sym is an aerobic, Gram-negative, non-spore-forming rod. This report reveals the genome of M. loti strain CJ3Sym currently comprises 70 scaffolds totaling 7,563,725 bp. The high-quality draft genome is arranged in 70 scaffolds of 71 contigs, contains 7,331 protein-coding genes and 70 RNA-only encoding genes, and is part of the GEBA-RNB project proposal

Patterns of media coverage repeated in online abuse on high-profile criminal cases

What relationship do the mainstream media have with online abuse on high-profile criminal cases? This article hopes to make a start at answering this question by examining tweets containing the #McCann hashtag, utilised by a highly engaged community of users to comment on all matters related to the disappearance of British child Madeleine McCann. On #McCann, the child’s parents and other players are often singled out as the perpetrators of her disappearance and other crimes, in a blend of harassment, defamation and insults with conspiracy theories, disinformation and a strong anti-establishment vein typical of the posttruth era. Through an experimental digital ethnography blending elements of content and discourse analysis, this research has observed the #McCann conversation and analysed 500 tweets with the hashtag, observing that some of the most offensive theories posted by users on Twitter reprised themes seen in the mainstream media at the time of the disappearance, which resulted in defamation lawsuits by the McCanns and in complaints about unethical reporting at the Leveson Inquiry. This raises questions about the mainstream media’s responsibility and duty of care towards people they report on in the digital age, and showcases a symbiotic yet diffident relationship between anti-establishment online users and traditional news media

The normalisation of Food Aid: What happened to feeding people well?

In the UK, food poverty has increased in the last 15 years and the food aid supply chain that has emerged to tackle it is now roughly 10 years old. In this time, we have seen the food aid supply chain grow at a rate that has astounded many.  Recently that growth has been aided by a grant of £20m from a large supermarket chain. It appears institutionalisation is just around the corner, if not already here. It also appears that there is far greater emphasis on dealing with  the symptoms as opposed to solving the root causes of the problem. As an opinion piece, this paper reflects on some of the prevalent issues, and suggests some ways forward

Mediated behavioural change in human-machine networks: exploring network characteristics, trust and motivation

Human-machine networks pervade much of contemporary life. Network change is the product of structural modifications along with differences in participant be-havior. If we assume that behavioural change in a human-machine network is the result of changing the attitudes of participants in the network, then the question arises whether network structure can affect participant attitude. Taking citizen par-ticipation as an example, engagement with relevant stakeholders reveals trust and motivation to be the major objectives for the network. Using a typology to de-scribe network state based on multiple characteristic or dimensions, we can pre-dict possible behavioural outcomes in the network. However, this has to be medi-ated via attitude change. Motivation for the citizen participation network can only increase in line with enhanced trust. The focus for changing network dynamics, therefore, shifts to the dimensional changes needed to encourage increased trust. It turns out that the coordinated manipulation of multiple dimensions is needed to bring about the desired shift in attitude.Comment: Paper submitted to SocInfo, organised by the Oxford Internet Institute, September 201

Extreme managers, extreme workplaces: capitalism, organizations and corporate psychopaths

This paper reports on in-depth, qualitative research carried out in England in 2013 among five organizational directors and two senior managers who had worked with other senior directors or managers who were Corporate Psychopaths, as measured by a management psychopathy measure. The Corporate Psychopaths reported on in this research displayed remarkable consistency in their approach to management to the extent that they could be called “text book examples” of managerial psychopathy. They were seen as being organizational stars and as deserving of performance awards by those above them, while the Corporate Psychopaths simultaneously subjected those below them to extreme forms of behavior, including bullying, intimidation and coercion and also engaged in extreme forms of mismanagement; such as very poor levels of personnel management, directionless leadership, miss-management of resources and outright fraud

Signal transduction in a covalent post-assembly modification cascade

Natural reaction cascades control the movement of biomolecules between cellular compartments. Inspired by these systems, we report a synthetic reaction cascade employing post-assembly modification reactions to direct the partitioning of supramolecular complexes between phases. The system is composed of a self-assembled tetrazine-edged FeII8L12 cube and a maleimide-functionalized FeII4L6 tetrahedron. Norbornadiene (NBD) functions as the stimulus that triggers the cascade, beginning with the inverse-electron-demand Diels–Alder reaction of NBD with the tetrazine moieties of the cube. This reaction generates cyclopentadiene as a transient by-product, acting as a relay signal that subsequently undergoes a Diels–Alder reaction with the maleimide-functionalized tetrahedron. Cyclooctyne can selectively inhibit the cascade by outcompeting NBD as the initial trigger. Initiating the cascade with 2-octadecyl NBD leads to selective alkylation of the tetrahedron upon cascade completion. The increased lipophilicity of the C18-tagged tetrahedron drives this complex into a non-polar phase, allowing its isolation from the initially inseparable mixture of complexes

Post-assembly modification of kinetically metastable Fe(II)2L3 triple helicates.

We report the covalent post-assembly modification of kinetically metastable amine-bearing Fe(II)2L3 triple helicates via acylation and azidation. Covalent modification of the metastable helicates prevented their reorganization to the thermodynamically favored Fe(II)4L4 tetrahedral cages, thus trapping the system at the non-equilibrium helicate structure. This functionalization strategy also conveniently provides access to a higher-order tris(porphyrinatoruthenium)-helicate complex that would be difficult to prepare by de novo ligand synthesis.This work was supported by the UK Engineering and Physical Sciences Research Council (EPSRC). D.A.R. acknowledges the Gates Cambridge Trust for Ph.D. (Gates Cambridge Scholarship) and conference funding.This is the final published version. It first appeared at http://pubs.acs.org/doi/abs/10.1021/ja5042397