Nuclear magnetic resonance (NMR) spectroscopy cannot be used to discriminate enantiomers, and NMR resonances of enantiomeric mixtures are generally not affected by enantiomeric excess (). Here, we report that a coordination complex (·2Zn·3), where is a salen-like prochiral ligand and is an exchangeable acetate coligand, exhibits symmetrical splitting of one of the H NMR resonances of with the degree of splitting linearly proportional to of the chiral guest coligand , 2-phenoxypropionic acid. Despite the well-defined chirality in the crystal structure of ·2Zn·3, concurrent fast chiral inversion and coligand exchange in solution renders ·2Zn·3 the primary example of prochiral solvating agent (-CSA) based on a coordination complex. Notably, the NMR resonances remain split even in dilute solution due to the lack of chiral guest dissociation in the coligand exchange system. This work provides new insights into chiral transfer events in metal-ligand complexes.
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Dalton Trans
December 2024
School of Chemical Sciences, The University of Auckland, Private Bag 92019, Auckland 1142, New Zealand.
[M(arene)(HQ)Cl] complexes (M = Ru/Os/Rh/Ir; HQ = 8-hydroxyquinoline) have shown promise as anticancer agents. To assess the effect of conjugating biotin (vitamin B7) to such compounds and improve their tumor-targeting ability through interaction with the sodium-dependent multivitamin transporter (SMVT), the chlorido co-ligand was exchanged with biotinylated 6-aminoindazole. The complexes were characterized by NMR spectroscopy and mass spectrometry, and purity was determined by elemental analysis.
View Article and Find Full Text PDFInorg Chem
September 2024
Faculty of Chemistry, University of Wrocław, F. Joliot-Curie 14, 50-383 Wrocław, Poland.
Optically pure ()- and racemic (/)--1,2-di(tetrazol-1-yl)cyclopentane were synthesized and used to prepare homo- and heterochiral Fe(II) coordination compounds. [Fe((/)-CHN)(CHCN)](BF) (), [Fe((/)-CHN)(CHCN)](BF) (), [Fe(()-CHN)(CHCN)](BF)·2CHCN (), and [Fe(()-CHN)(CHCN)](BF) () form a family of one-dimensional coordination polymers. Fe(II) cations in these complexes are characterized by a heteroleptic coordination environment: the neighboring metal centers are bridged by two 1,2-di(tetrazol-1-yl)cyclopentane molecules, while the nitrile molecules (acetonitrile or propionitrile, respectively) occupy the axial positions.
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August 2024
Department of Chemical Sciences, IISER Mohali, Sector-81, Knowledge city, S.A.S. Nagar, Mohali-140306, Punjab, India.
Detailed state-of-the-art and density functional theory (DFT) calculations have been undertaken to understand both Single-Molecule Magnetic (SMM) and Single-Molecule Toroic (SMT) behaviors of fascinating 3d-4f {MLn} triangular complexes having the molecular formula [MII3LnIII3(O)L(PyCO)](OH)(ClO)·8HO (with M = Zn; Ln = Dy (1), Tb (2) & Gd (3) and M = Cu; Ln = Dy (4), Tb (5) & Gd (6)) and [NiLn(HO)(mpko)(O)(NO)](ClO)3CHOH3CHCN (Ln = Dy (7), Tb (8), and Gd (9)) [mpkoH = 1-(pyrazin-2-yl)ethanone oxime]. All these complexes possess a peroxide ligand that bridges the {LnIII3} triangle in a μ-η:η fashion and the oxygen atoms/oxime of co-ligands that connect each M ion to the {LnIII3} triangle. Through our computational studies, we tried to find the key role of the peroxide bridge and how it affects the SMM and SMT behavior of these complexes.
View Article and Find Full Text PDFInorg Chem
July 2024
Department of Chemistry, Indian Institute of Technology Bombay, Powai, Mumbai 400076, India.
The article demonstrated diverse binding modes of deprotonated 1,3-di(2-pyridinyl)-1,3-propanedione (HL) (κ-[O,O], κ-[N,O], and μ-bis-κ-[N,O]) on selective ruthenium platforms: Ru(acac) (dimeric []ClO), Ru(bpy) (monomeric []ClO), Ru(pap) (isomeric monomeric []ClO/[]ClO, dimeric [](ClO)), and Ru(PPh)(CO) (monomeric , isomeric dimeric []ClO/[]ClO) (acac = acetylacetonate, bpy = 2,2-bipyridine, pap = 2-phenylazopyridine). Structural authentication of the complexes revealed (i) diverse binding mode of L including its unprecedented bridging mode in []ClO, (ii) varying degrees of nonplanarity of L, and (iii) development of 1D polymeric chains or dimeric/tetrameric forms via intermolecular π-π interactions. The preferential binding feature of L in the complexes could also be corroborated by their calculated relative energies.
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April 2024
Key Laboratory of Bioinorganic and Synthetic Chemistry, Ministry of Education, School of Chemistry, IGCME, GBRCE for Functional Molecular Engineering, Sun Yat-Sen University, Guangzhou 510275, P. R. China.
A series of two-dimensional (2D) spin-crossover coordination polymers (SCO-CPs) [Fe(TPE)(NCX)]·solv (1: X = BH, solv = HO·2CHOH·DMF; 2: X = Se, solv = HO·2CHOH·0.5DMF; 3: X = S, solv = HO·2CHOH·0.5DMF) were synthesized by employing 1,1,2,2-tetra(pyridin-4-yl)ethene (TPE) and pseudohalide (NCX) coligands.
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