Herein we present the first double deprotonation of acetonitrile (CHCN) using two equivalents of a bimetallic iron-aluminium complex. The products of this reaction contain an exceeding simple yet rare [CHCN] dianion moiety that bridges two metal fragments. DFT calculations suggest that the bonding to the metal centres occurs through heavily polarised covalent interactions. Mechanistic studies reveal the intermediacy of a monomeric [CHCN] complex, which has been characterised in situ. Our findings provide an important example in which a bimetallic metal complex achieves a new type of reactivity not previously encountered with monometallic counterparts. The isolation of a [CHCN] dianion through simple deprotonation of CHCN also offers the possibility of establishing a broader chemistry of this motif.
Download full-text PDF |
Source |
---|---|
http://www.ncbi.nlm.nih.gov/pmc/articles/PMC10952947 | PMC |
http://dx.doi.org/10.1002/ange.202219212 | DOI Listing |
Chemistry
December 2024
Uppsala Universitet Teknisk-naturvetenskapliga vetenskapsomradet: Uppsala Universitet Teknisk-naturvetenskapliga fakulteten, Chemistry - Angstrom, BOX 523, 57120, Uppsala, SWEDEN.
This experimental and theoretical study illustrates how phosphaalkenes, which are isolobal to alkenes, can utilize a variety of external triggers for molecular switching. The E/Z isomerization of a truxene-based phosphaalkene, i.e.
View Article and Find Full Text PDFOrg Biomol Chem
December 2024
Université de Reims Champagne-Ardenne, CNRS, ICMR, Reims, France.
A strategy for the synthesis of 1--substituted thioglycals was developed from cyclic carbohydrate-derived ketene dithioacetals in a four-step sequence. The corresponding thioglycals, in two carbohydrate series, were first obtained by removal of the exocyclic glycosyl sulfoxide, followed by treatment with an organolithium reagent. Various electrophilic groups were introduced onto the thioglycal double bond after deprotonation and formation of a glycosyl lithium intermediate.
View Article and Find Full Text PDFJ Agric Food Chem
December 2024
CAS Key Laboratory of Environmental and Applied Microbiology, Environmental Microbiology Key Laboratory of Sichuan Province, Chengdu Institute of Biology, Chinese Academy of Sciences, Chengdu 610041, China.
BcABA3 is an unusual sesquiterpene synthase that lacks the conserved DDxxD and DTE/NSE motifs. Despite this, it can catalyze the conversion of farnesyl diphosphate to 2Z,4E-α-ionylideneethane. We used structure prediction, multiscale simulations, and site-directed mutagenesis experiments to investigate BcABA3 and its catalytic mechanism.
View Article and Find Full Text PDFSmall
December 2024
State Key Laboratory of Inorganic Synthesis and Preparative Chemistry, College of Chemistry, Jilin University, Changchun, Jilin, 130012, China.
Defect engineering is widely regarded as a promising strategy to enhance the performance of electrocatalysts for water splitting. In this work, defective NiFe layered double hydroxide (NiFe LDH) with a high density of edge sites (edge-rich NiFe LDH) is synthesized via a simple reduction process during the early stages of nucleation. The introduction of edges into oxygen evolution reaction (OER) catalysts modulates the electronic structure of the active sites.
View Article and Find Full Text PDFInt J Mol Sci
November 2024
Core Facility Center 'Arktika', Northern (Arctic) Federal University, Arkhangelsk 163002, Russia.
N,N'-Dialkylimidazolium-based ionic liquids are capable of completely dissolving lignocellulosic biomass at elevated temperatures and are considered as promising green solvents for future biorefining technologies. However, the obtained ionic liquid lignin preparations may contain up to several percent nitrogen. This indicates strong interactions between the biopolymer and the IL cation, the nature of which has not yet been clarified.
View Article and Find Full Text PDFEnter search terms and have AI summaries delivered each week - change queries or unsubscribe any time!