Development of molecular cluster models to probe pyrite surface reactivity.

The recent discovery that anaerobic methanogens can reductively dissolve pyrite and utilize dissolution products as a source of iron and sulfur to meet their biosynthetic demands for these elements prompted the development of atomic-scale nanoparticle models, as maquettes of reactive surface sites, for describing the fundamental redox steps that take place at the mineral surface during reduction. The given report describes our computational approach for modeling n(FeS2 ) nanoparticles originated from mineral bulk structure. These maquettes contain a comprehensive set of coordinatively unsaturated Fe(II) sites that are connected via a range of persulfide (S2 2- ) ligation. In addition to the specific maquettes with n = 8, 18, and 32 FeS2 units, we established guidelines for obtaining low-energy structures by considering the pattern of ionic, covalent, and magnetic interactions among the metal and ligand sites. The developed models serve as computational nano-reactors that can be used to describe the reductive dissolution mechanism of pyrite to better understand the reactive sites on the mineral, where microbial extracellular electron-transfer reactions can occur.

A naturalist perspective of microbiology: Examples from methanogenic archaea.

Storytelling has been the primary means of knowledge transfer over human history. The effectiveness and reach of stories are improved when the message is appropriate for the target audience. Oftentimes, the stories that are most well received and recounted are those that have a clear purpose and that are told from a variety of perspectives that touch on the varied interests of the target audience. Whether scientists realize or not, they are accustomed to telling stories of their own scientific discoveries through the preparation of manuscripts, presentations, and lectures. Perhaps less frequently, scientists prepare review articles or book chapters that summarize a body of knowledge on a given subject matter, meant to be more holistic recounts of a body of literature. Yet, by necessity, such summaries are often still narrow in their scope and are told from the perspective of a particular discipline. In other words, interdisciplinary reviews or book chapters tend to be the rarity rather than the norm. Here, we advocate for and highlight the benefits of interdisciplinary perspectives on microbiological subjects.

High-Spin Imido Cobalt Complexes with Imidyl Radical Character*.

We report on the synthesis of a variety of trigonal imido cobalt complexes [Co(NAryl)L2 ]- , (L=N(Dipp)SiMe3 ), Dipp=2,6-diisopropylphenyl) with very long Co-NAryl bonds of around 1.75 Å. Their electronic structure was interrogated using a variety of physical and spectroscopic methods such as EPR or X-Ray absorption spectroscopy which leads to their description as highly unusual imidyl cobalt complexes. Computational analyses corroborate these findings and further reveal that the high-spin state is responsible for the imidyl character. Exchange of the Dipp substituent on the imide by the smaller mesityl function (2,4,6-trimethylphenyl) effectuates the unexpected Me3 Si shift from the ancillary ligand set to the imidyl nitrogen, revealing a highly reactive, nucleophilic character of the imidyl unit.

A new cross-conjugated mesomeric betaine.

Cross-conjugated mesomeric betaine (CCMB) has been defined as the dipolar species in which positive and negative charges are exclusively restricted to different parts of the molecule. In contrast to indolizine which undergoes [8+2] cycloaddition with dimethyl acetylenedicarboxylate (DMAD), its 1-aza analogue, namely imidazo[1,2-a]pyridine reacts with the same reagent to afford the first representative of the CCMB isoconjugate with the odd non-alternant hydrocarbon anion. The structure of the product could be assigned on the basis of the NMR and HRMS results. Furthermore, the spectral studies indicated the presence of additional DMAD molecules in CCMB, possibly in the form of a charge-transfer (CT) complex. The whole sequence of reactions initiated by the attack of imidazo[1,2-a]pyridine on DMAD could be rationalized on the basis of the computational study of a model reaction sequence at the DFT (B3LYP/6-31+G(d)) level indicating the formation of a new CCMB derivative. The electronic excited states of the product were investigated by time-dependent density functional theory (TDDFT) calculations at the wB97XD/6-311++G(d,p) level, which indicate low-lying charge transfer that is characteristic of the CCMBs.

Synergy between Experimental and Theoretical Results of Some Reactions of Annelated 1,3-Azaphospholes.

Computational calculations have been used successfully to explain the reactivity of the >C=P- functionality in pyrido-annelated 1,3-azaphospholes. Theoretical investigation at the Density Functional Theory (DFT) level shows that the lone pair of the bridgehead nitrogen atoms is involved in extended conjugation, due to which electron density increases considerably in the five-membered azaphosphole ring. The electron density in the azaphosphole is further enhanced by the presence of an ester group at the 3-position making the >C=P- functionality electron-rich. Thus, 1,3-azaphospholo[5,1-a]pyridine, i.e., 2-phosphaindolizine having ester group at the 3-position only does not undergo Diels-Alder (DA) reaction with an electron rich diene, such as 2,3-dimethyl-1,3-butadiene (DMB). However, an ester group at 1-position acts as electron-sink, due to which transfer of the electron density to the >C=P- moiety is checked and DA reaction occurs across the >C=P- functionality. The coordination of the Lewis acid to the carbonyl group at the 3-position raises the activation barrier, while it is lowered remarkably when it is coordinated to the P atom. Furthermore, the attack of 1,3-butadiene on the Si face of the P-coordinated (o-menthoxy)aluminum dichloride complex is a lower activation energy path. Fukui functions could be used to explain relative reactivities of indolizine and 2-phosphaindolizine towards electrophilic substitution reactions.