01711nas a2200253   4500008004100000022001400041245005700055210005600112260000800168300001500176490000700191520099700198653001701195653000801212653002201220653000901242100001801251700001701269700002501286700001701311700001901328700001901347856009101366       2023                        eng d  a1434-194800aSix-membered NHC stabilized monomeric zinc complexes0 aSixmembered NHC stabilized monomeric zinc complexes  cJUL  ae2023001670 v263 a<p>
	This paper describes the rare use of a 6-membered saturated N-heterocyclic carbene (NHC) known as 1,3-di(2,6-diisopropylphenyl) tetrahydropyrimidine-2-ylidene (abbreviated as 6-SI-Dipp) as a ligand in zinc chemistry. We report on the investigation of the reactions between 6-SI-Dipp and ZnX2, which resulted in a range of new monomeric 6-SIDipp center dot ZnX2 complexes (X=Et (1), Cl (2), Br (3), and I (4)). We also prepared a new NHC zinc complex where the two substituents of the zinc atom are different, 6-SIDipp center dot Zn(Et)Br (7) through the reaction of the proligand [6-SIDippH]Br with ZnEt2. We have observed that the reactions of complex 1 with sulfur and HBpin led to the removal of the ZnEt2 moiety, resulting in the formation of a C=S double bond and a B H activation product, respectively. Lastly, the reaction of 1 with five-membered NHCs led to the exchange of carbene and the formation of either 5-IDipp center dot ZnEt2 (8) or 5-SIDipp center dot ZnEt2 (9).</p>
10aLewis adduct10aNHC10aX-ray diffraction10azinc1 aGour, Kritika1 aKundu, Gargi1 aDash, Soumya, Ranjan1 aVanka, Kumar1 aTothadi, Srinu1 aSen, Sakya, S.  uhttp://library.ncl.res.in/content/six-membered-nhc-stabilized-monomeric-zinc-complexes02138nas a2200193   4500008004100000022001400041245008200055210006900137260000800206300001400214490000700228520150100235100002501736700002101761700002701782700001501809700001701824856010301841       2024                        eng d  a0020-166900aSize matters: computational insights into the crowning of noble gas trioxides0 aSize matters computational insights into the crowning of noble g  cFEB  a4099-41070 v633 a<p>
	In pursuit of enhancing the stability of the highly explosive and shock-sensitive compound XeO3, we performed quantum chemical calculations to investigate its possible complexation with electron-rich crown ethers, including 9-crown-3, 12-crown-4, 15-crown-5, 18-crown-6, and 21-crown-7, as well as their thio analogues. Furthermore, we expanded our study to other noble gas trioxides (NgO(3)), namely, KrO3 and ArO3. The basis set superposition error (BSSE) corrected interaction energies for these adducts range from -13.0 kcal/mol to -48.2 kcal/mol, which is notably high for sigma-hole-mediated noncovalent interactions. The formation of these adducts was observed to be more favorable with the increase in the ring size of the crowns and less favorable while going from XeO3 to ArO3. A comprehensive analysis by various computational tools such as the mapping of the electrostatic potential (ESP), Wiberg bond indices (WBIs), Bader's theory of atoms-in-molecules (AIM), natural bond orbital (NBO) analysis, noncovalent interaction (NCI) plots, and energy decomposition analysis (EDA) revealed that the C-H center dot center dot center dot O interactions, as well as dispersion interactions, play a pivotal role in stabilizing adducts involving larger crowns. A noteworthy outcome of our study is the revelation of a coordination number of 9 for xenon in the complex formed between XeO3 and the thio analogue of 18-crown-6, which is higher than the largest number reported to date.</p>
1 aDash, Soumya, Ranjan1 aSharma, Himanshu1 aTiwari, Mrityunjay, K.1 aGreb, Lutz1 aVanka, Kumar  uhttp://library.ncl.res.in/content/size-matters-computational-insights-crowning-noble-gas-trioxides