Search results for "Effects"

1976

tert-Butoxy radicals were generated by decomposing di-tert-butyl hyponitrite. The relative reactivities of substrates were measured from the ratio of tert-butanol and acetone formed. Polystyrene was found to be less reactive than model compounds. Activation parameters for the hydrogen abstraction reaction for cumene, 3-phenylpentane, and 2,4-diphenylpentane are reported and show small differences for the enthalpy of activation; large negative values for the entropy of activation demonstrate the importance of steric hindrance in the hydrogen abstracting step. 2,3-Diphenylbutane as model compound for head to head links in polystyrene exhibits low reactivity, whereas 2,5-diphenylhexane, a mode…

Unveiling the Ionic Diels-Alder Reactions within the Molecular Electron Density Theory

2021

The ionic Diels–Alder (I-DA) reactions of a series of six iminium cations with cyclopentadiene have been studied within the Molecular Electron Density Theory (MEDT). The superelectrophilic character of iminium cations, ω &gt

Ligand Effects on the Chemoselectivity of Ortho-Metalated Rhodium(II) Catalyzed α-Diazo Ketone Transformations

1997

Rh2(OOCR)2(PC)2 complexes (PC = orthometalated phosphines, OOCR = carboxylates) with very polarizable ligands, such as aromatic rings directly joined to the rhodium atoms, control chemoselectivity in competitive metal carbene transformations of α-diazo ketones. These catalysts have a mixed set of ligands that allows choosing among a big selection of ligands to gradually affect the electronic and steric properties of the catalyst. Their selectivity depends on the electrophilicity of the ligands and the polarizability of the metalated aromatic rings. Thus, Rh2(OOCR)2(PC)2 compounds [PC = (C6H4)P(CH3)(C6H5), (p-CH3C6H3)P(p-CH3C6H4)2, (C6H4)P(C6H5)2; R = C3F7 or CF3] exhibit an exceptional sele…

Uncommon coordination behaviour of P(S) and P(Se) units when bonded to carboranyl clusters: experimental and computational studies on the oxidation o…

2010

Oxidation of closo-carboranyl diphosphines 1,2-(PR(2))(2)-1,2-closo-C(2)B(10)H(10) (R=Ph, iPr) and closo-carboranyl monophosphines 1-PR(2)-2-R'-1,2-closo-C(2)B(10)H(10) (R=Ph, iPr, Cy; R'=Me, Ph) with hydrogen peroxide, sulfur and elemental black selenium evidences the unique capacity of the closo-carborane cluster to produce uncommon or unprecedented P/P(E) (E=S, Se) and P=O/P=S chelating ligands. When H(2)O(2) reacts with 1,2-(PR(2))(2)-1,2-closo-C(2)B(10)H(10) (R=Ph, iPr), they are oxidized to 1,2-(OPR(2))(2)-1,2-closo-C(2)B(10)H(10) (R=Ph, iPr). However, when S and Se are used, different reactivity is found for 1,2-(PPh(2))(2)-1,2-closo-C(2)B(10)H(10) and 1,2-(PiPr(2))(2)-1,2-closo-C(2)…

Remarkable Steric Effects and Influence of Monodentate Axial Ligands L on the Spin-Crossover Properties of trans-[FeII(N4 ligand)L] Complexes

2007

Iron(II) complexes obtained from tetradentate, rigid, linear N4 ligands have been investigated to appraise the influence of steric effects and the impact of trans-coordinated anions on the spin-transition behavior. As expected, the well-designed ligands embrace the metal center, resulting in octahedral iron(II) complexes where the basal plane is fully occupied by the pyridine/pyrazole N4 ligand, while anions or solvent molecules are exclusively axially coordinated. Precursor complexes, namely, [Fe(bpzbpy)(MeOH)2](BF4)2 (where bpzbpy symbolizes the ligand 6,6'-bis(N-pyrazolylmethyl)-2,2'-bipyridine) and [Fe(mbpzbpy)(MeOH)2](BF4)2 (where mbpzbpy symbolizes the ligand 6,6'-bis(3,5-dimethyl-N-p…

Activation of the Cyano Group at Imidazole via Copper Stimulated Alcoholysis

2019

Reactions of 4,5-dicyano-1-methylimidazole with CuX2 (X = Cl, Br) in alcohol solvents (ethanol and methanol) resulted in the formation of Cu(II) carboximidate complexes [CuCl2(5- cyano-4-C(OEt)N-1-methylimidazole)(EtOH)] (1), [Cu2(&micro

Direct High-Performance Liquid Chromatographic Separation of Peptide Enantiomers:  Study on Chiral Recognition by Systematic Evaluation of the Influe…

2002

All-R/all-S enantiomers of oligoalanines (Ala(n), n = 1-10) with N-terminal protection group have been separated by HPLC on chiral stationary phases based on various cinchona alkaloid selectors. Structure-enantioselectivity relationships derived by extensive selector structure optimization provided insights into binding mechanisms and chiral recognition. Their interpretation was supported by X-ray crystal structures of amino acid and dipeptide, respectively, in complex with chiral selector. Optimized selectors have bulky elements representing steric barriers and deep binding pockets that afforded very high enantioselectivities; e.g., for the all-R and all-S enantiomers of N-(3,5-dinitrobenz…

Unveiling the regioselectivity in electrophilic aromatic substitution reactions of deactivated benzenes through molecular electron density theory

2021

The origin of the meta regioselectivity in electrophilic aromatic substitution (EAS) reactions of deactivated benzene derivatives is herein analysed through Molecular Electron Density Theory (MEDT). To this end, the EAS reaction of benzenesulfonic acid with the nitronium NO2+ ion in H2SO4 solution has been studied at the ωB97X-D/6-311G(d,p) level. This reaction takes place through a two-step polar mechanism involving the formation of an unstable cation intermediate. The activation Gibbs free energies associated with the three competitive regioisomeric reaction paths are found in the narrow range of 15.5–18.3 kcal mol−1. By using the Eyring–Polanyi equation a relationship of 18.7 (ortho) : 8…

Steric interactions controlling the syn diastereofacial selectivity in the [3 + 2] cycloaddition reaction between acetonitrile oxide and 7-oxanorborn…

2017

A Molecular Electron Density Theory study of the zw-type 32CA reactions of acetonitrile oxide (NO) with two 7-oxanorborn-5-en-2-ones (ONBs) has been performed at the DFT B3LYP/6-31G(d) computational level. These cycloadditions proceed through one-step mechanisms with high activation energies and present low para regio and complete syn diastereofacial selectivities. While the non-polar character of these zw-type 32CA reactions, which is the consequence of the insufficient electrophilic activation of ONBs, according to the analysis of the conceptual DFT reactivity indices, accounts for the high activation energies, and low para regioselectivity, NCI topological analyses at the anti/syn pairs …

Ethylene oligomerization with 2-hydroxymethyl-5,6,7-trihydroquinolinyl-8-ylideneamine-Ni(II) chlorides

2021

Abstract A series of Ni complexes of the general formula [2-(MeOH)-8-{N(Ar)}C9H8N]NiCl2, where Ar = 2,6-Me2C6H3 in Ni1; 2,6-Et2C6H3 in Ni2; 2,6-i-Pr2C6H3 in Ni3; 2,4,6-Me3C6H2 in Ni4; 2,6-Et2-4-MeC6H2 in Ni5 and 2,4,6-t-Bu3C6H2 in Ni6 has been synthesized and characterized by elemental analysis and IR spectroscopy. On activation with MMAO or Et2AlCl, these complexes showed high activity in ethylene oligomerization, reaching 2.23 × 106 g·mol–1 (Ni) h–1 at 30 °C with the Al/Ni ratio of 5500 and 9.11 × 105 g·mol–1 (Ni) h–1 with the Al/Ni of 800, respectively. Moreover, the content of α-C4 indicated high selectivity exceeding 99% in the Ni/Et2AlCl system. Comparing with the previous report by o…