Bonding and stability of dinitrogen-bonded donor base-stabilized Si(0)/Ge(0) species [(cAACMe-Si/Ge)2(N2)]: EDA-NOCV analysis.

Recently, dinitrogen (N2) binding and its activation have been achieved by non-metal compounds like intermediate cAAC-borylene as (cAAC)2(B-Dur)2(N2) [cAAC = cyclic alkyl(amino) carbene; Dur = aryl group, 2,3,5,6-tetramethylphenyl; B-Dur = borylene]. It has attracted a lot of scientific attention from different research areas because of its future prospects as a potent species towards the metal free reduction of N2 into ammonia (NH3) under mild conditions. Two (cAAC)(B-Dur) units, each of which possesses six valence electrons around the B-centre, are shown to accept σ-donations from the N2 ligand (B ← N2). Two B-Dur further provide π-backdonations (B → N2) to a central N2 ligand to strengthen the B-N2-B bond, providing maximum stability to the compound (cAAC)2(B-Dur)2(N2) since the summation of each pair wise interaction accounted for the total stabilization energy of the molecule. (cAAC)(B-Dur) unit is isolobal to cAAC-E (E = Si, Ge) fragment. Herein, we report on the stability and bonding of cAAC-E bonded N2-complex (cAAC-E)2(N2) (1-2; Si, Ge) by NBO, QTAIM and EDA-NOCV analyses (EDA-NOCV = energy decomposition analysis coupled with natural orbital for chemical valence; QTAIM = quantum theory of atoms in molecule). Our calculation suggested that syntheses of elusive (cAAC-E)2(N2) (1-2; Si, Ge) species may be possible with cAAC ligands having bulky substitutions adjacent to the CcAAC atom by preventing the homo-dimerization of two (cAAC)(E) units which can lead to the formation of (cAAC-E)2. The formation of E[double bond, length as m-dash]E bond is thermodynamically more favourable (E = Si, Ge) over binding energy of N2 inbetween two cAAC-E units.

Recent advances in cascade reactions and their mechanistic insights: a concise strategy to synthesize complex natural products and organic scaffolds.

The beauty of cascade reactions to bestow us with cumbersome organic scaffolds has made them a cutting-edge area of research. Although the planning of cascades may require intuition, their results can be highly impactful. The development of cascades to provide specific targeted molecules of an appropriate structural and stereochemical framework poses a significant challenge but can serve as one of the most impressive tools in organic synthesis. This review shares a broad interest in compiling cascade transformations towards the construction of polycyclic frameworks, induction of chirality/asymmetry in the protocol, etc. to solve diverse challenges in organic synthesis pursuits, as cascades enable the rapid and efficient construction of complex architectures from simple molecules. The studies highlighted herein manifest the utilization of a range of cascade reactions under various classifications for generating natural product skeletons such as palau'amine, benzosimuline, arcutinine, and others from simple building blocks, with emphasis on breakthroughs and potential for asymmetric synthesis. The exquisite synthetic designs of recently completed total synthesis of natural products with a focus on strategic concerns are also highlighted in this review.

The cultural education of academic evaluators: lessons from a university-Hmong community partnership.

This article explores some of the lessons a university-based evaluation team learned while attempting to hire, retain, and work with staff members from a local Hmong community. These staff members were hired to assist a federally-funded community collaborative with implementing and evaluating a family strengthening program for Hmong families with adolescents. Over the course of two years, a succession of individuals were hired and resigned from a key staff position. These resignations occurred at critical points in the project, undermining a critical component of the program's evaluation. Through interviews, observations, self-reflection, and feedback from colleagues and reviewers, a better understanding of the reasons for these difficulties began to emerge. The challenges examined in this article help to illustrate some of the complexities faced by academics when conducting a community-based project with an underserved racial ethnic population. The article concludes by discussing some of the lessons learned and what they might suggest for others doing similar types of work.