B₁₂ is a rigid cluster with high inner ring rotational energy barrier. However, doping it Ir lowers the barrier significantly, transforming IrB₁₂⁻ in Wankel motor.

Selective reduction of CO2 is an efficient solution for producing nonfossil-based chemical feedstocks and simultaneously alleviating the increasing atmospheric concentration this greenhouse gas. With aim, molecular electrocatalysts are being extensively studied, although selectivity remains issue. In work, a combined experimental-computational study explores how structure Mn-based complexes determines dominant product in to HCOOH, CO, H2. contrast previous Mn(bpy-R)(CO)3Br catalysts...

A series of clusters with the general formula CBe(5)E(-) (E = Al, Ga, In, Tl) are theoretically shown to have a planar pentacoordinate carbon atom. The structures show simple and rigid topological framework-a EBe(4) ring surrounding C center, one Be-Be bonds capped in-plane by fifth Be system is stabilized network multicenter σ in which central atom acceptor, π systems as well donates charge E atoms that encircle it.

Can relativistic effects modify the NICS and B(ind) values? In this manuscript we evaluate corrections incorporated via zeroth-order regular approximation to calculations of nucleus-independent chemical shifts induced magnetic field (B(ind)) in E12(2-) spherenes (E = Ge, Sn, Pb). We found that both electron delocalization descriptors are strongly affected by corrections. For instance, for plumbaspherene, difference values from nonrelativistic relativity-included calculation is almost 40 ppm!...

Ab initio molecular dynamics simulations are used to explore tetrahydrofuran (THF) solutions containing pure LiCl and with CH3MgCl, as model constituents of the turbo Grignard reagent. aggregates Li4Cl4, which preferentially assumes compact cubane-like conformations. In particular, an open-edge pseudotetrahedral frame is promoted by solvent-assisted Li-Cl bond cleavage. Among species involved in Schlenk equilibrium, prefers coordinate MgCl2 through μ2-Cl bridges. Using a 1:1 Li:Mg ratio,...

By using two potential tridentate ligands, HL1 [4-chloro-2-[(2-morpholin-4-yl-ethylimino)-methyl]-phenol] and HL2 [4-chloro-2-[(3-morpholin-4-yl-propylimino)-methyl]-phenol], which differ by one methylene group in the alkyl chain, four new ZnII complexes, namely, [Zn(L2H)2](ClO4)2 (1), [Zn(L1)(H2O)2][Zn(L1)(SCN)2] (2), [Zn(L1)(dca)]n (3), [Zn2(L1)2(N3)2(H2O)2] (4) [where dca = dicyanamide anion] were synthesized structurally characterized. The results indicate that slight structural...

The halogen bond (XB) is a highly directional class of noncovalent interactions widely explored by experimental and computational studies. However, the NMR signature XB has attracted limited attention. prediction analysis solid-state (SSNMR) chemical shift tensor provide useful strategies to better understand interactions. In this work, we employ protocol for modeling analyzing 19F SSNMR shifts previously measured in family square-planar trans NiII-L2-iodoaryl-fluoride (L = PEt3) complexes...

Abstract Inverse carbon‐free sandwich structures with formula E 2 P 4 (E=Al, Ga, In, Tl) have been proposed as a promising new target in main‐group chemistry. Our computational exploration of their corresponding potential‐energy surfaces at the S12h/TZ2P level shows that indeed stable inverse‐sandwiches can be obtained if one chooses an appropriate Group 13 element for E. The boron analogue B does not form D h ‐symmetric inverse‐sandwich structure, but instead prefers d structure two...

We report a combined experimental-theoretical study on the 31P NMR chemical shift for number of trans-platinum(ii) complexes. Validity and reliability calculations are examined by comparing with experimental data. A successful computational protocol accurate prediction shifts was established trans-[PtCl2(dma)PPh3] (dma = dimethylamine) The computed values is shown to be critically dependent level relativistic effects (two-component vs. four component), choice density functionals, dynamical...

1H NMR spectroscopy has become an important technique for the characterization of transition-metal hydride complexes, whose metal-bound hydrides are often difficult to locate by X-ray diffraction. In this regard, accurate prediction chemical shifts provides a useful, but challenging, strategy help in interpretation experimental spectra. work, we establish density-functional-theory protocol that includes relativistic, solvent, and dynamic effects at high level theory, allowing us report...

The transfer hydrogenation of N-heterocyclic carbene (NHC)-supported diborenes with dimethylamine borane proceeds high selectivity for the trans-1,2-dihydrodiboranes. DFT calculations, supported by kinetic studies and deuteration experiments, suggest a stepwise proton-first-hydride-second reaction mechanism via an intermediate μ-hydrodiboronium dimethylaminoborate ion pair.

In the present study, we have theoretically analyzed supramolecular complexes based on Watson–Crick A–T and A–U base pairs using dispersion-corrected density functional theory (DFT).

Platinum-based anticancer drugs are actively developed utilizing lipophilic ligands or drug carriers for the efficient penetration of biomembranes, reduction side effects, and tumor targeting. We report development a supramolecular host-guest system built on cationic platinum(II) compounds bearing anchored in cavity macrocyclic host. The binding hydrolysis process platinum core were investigated detail by using NMR, MS, X-ray diffraction, relativistic DFT calculations. encapsulation...

We report here a systematic study on the ability of molecular cages to bind (transition) metals. Starting from superferrocenophane we investigate incorporation first-row transition metal (Sc–Zn) and alkaline-earth (Mg, Ca) double cations into these supermetallocenophane (super[5]phane) cages, compare them with corresponding metallocenes (Inorg. Chim. Acta, 2007, 360, 179). Moreover, also binding neutral double-cationic metals inside supermetallocyclophane (super[6]phane) cages. The...

Abstract Die Transferhydrierung von NHC‐stabilisierten Diborenen mit Dimethylamminboran verläuft hoher Selektivität zu trans‐1,2‐Dihydrodiboranen. DFT‐Rechnungen, unterstützt durch Kinetik‐ und Deuterierungsexperimente, lassen auf einen schrittweisen Reaktionsmechanismus schließen, bei dem zuerst das Proton anschließend Hydrid über ein μ‐Hydrodiboronium‐Dimethylaminoborat‐Ionenpaar als Zwischenstufe übertragen werden.

The incarceration of o-benzyne and 27 other guest molecules within hemicarcerand 1, as reported experimentally by Warmuth, Cram co-workers, has been studied density functional theory (DFT). 1 H NMR chemical shifts, rotational mobility, conformational preference the guests supramolecular cage were determined, which showed intriguing correlations shifts with structural parameters host-guest system. Furthermore, based on computed reassignments some signals are proposed. This affects, in...

We have employed computational methods to investigate the iridium-catalyzed allylic substitution leading formation of enantioenriched allyl carbamates from carbon dioxide (CO2). The reaction occurs in several steps, with initial an iridium-allyl, followed by nucleophilic attack carbamate formed situ CO2 and amine. A detailed isomeric analysis shows that rate-determining step differs for (R)- (S)-pathways. These insights are essential understanding reactions involving enantioselective CO2.

In this study, the electrocatalytic reduction of carbon dioxide by MnI, ReI, and RuII bipyridine complexes bearing pendant amines is evaluated DFT methods. Prior experimental studies showed that introducing in secondary coordination sphere catalyst shifts product selectivity from CO to HCOO– (in presence a proton source) case Mn. contrast, major with Re Ru. This work includes comprehensive study pathways leading CO, HCOO–, H2 elucidate energetic preferences underlie selectivity. Our results...

Enzymes in nature, such as the copper-based lytic polysaccharide monooxygenases (LPMOs), have gained significant attention for their exceptional performance C-H activation reactions. The use of H

F NMR parameters are versatile probes for studying metal-fluoride complexes. Quantum chemical calculations of

Ab initio molecular dynamics simulations are used to explore tetrahydrofuran (THF) solutions containing pure LiCl, and LiCl with CH3MgCl, as model constituents of the turbo Grignard reagent. aggregates Li4Cl4, which preferentially assumes compact cubane-like conformations. In particular, an open-edge pseudo tetrahedral frame is promoted by solvent-assisted Li-Cl bond cleavage. Among species involved in Schlenk equilibrium, prefers coordinating MgCl2 through m-Cl bridges. Using a 1:1 Li:Mg...

We have harnessed biomass-derived molecules to create sustainable phosphine ligands for catalysis. These renewable exhibit high activity in Pd-catalyzed cross-couplings, opening new avenues the late-stage modification of pharmaceuticals.

A series of three neutral, hexacoordinate tin(IV) complexes were synthesized by the reaction 4,4'‐dimethyl‐2,2'‐bipyridine (DMB) with SnX 4 , X = Cl, Br, and I, as starting materials. The (DMB)SnX characterized in solution 1 H, 13 C, 119 Sn NMR spectroscopy, solid‐state MAS spectroscopy. In addition, single‐crystal X‐ray diffraction elemental analysis used to confirm molecular structures. these complexes, tin atom adopts a distorted octahedral arrangement DMB acts bidentate N,N '‐chelate...