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Vol 45, No 10 (2019)
- Year: 2019
- Articles: 10
- URL: https://journals.rcsi.science/1070-3284/issue/view/13372
Article
Magnetic Properties of the Dicationic Iron o-Quinone Complexes with the Pyridinophane Ligands: A Quantum Chemical Study
Abstract
Computer modeling of the dicationic iron o-benzoquinone complexes with the 2,11-diaza[3.3]-(2,6)pyridinophane ligands is performed. The ground states of the studied compounds are the low-spin isomers. Strong antiferromagnetic exchange interactions are predicted to take place between lone electrons of the trivalent iron ion and the radical-anionic form of the redox-active ligand. The compound capable of undergoing crossover is revealed by the variation of substituents in the tetraazamacrocyclic base.
675-679
Comparison of Experimental and Experimental–Theoretical Topological Characteristics of the Electron Density in the Crystalline Complex η6-[3-Acetyltetrahydro-6-Phenyl-2Н-1,3-oxazine]tricarbonylchromium(0)
Abstract
Experimental and experimental–theoretical studies (using the molecular invariom) of the electron density distribution are performed for the η6-[3-acetyltetrahydro-6-phenyl-2Н-1,3-oxazine]tricarbonylchromium(0) complex. The topological characteristics of the electron density (ρ(r), ∇2ρ(r)) at the critical points (3, –1) coincide in the experimental and experimental–theoretical distributions within the “transferability indices.” The experimental–theoretical study more reliably localizes the “expected” critical points (3, –1) between the chromium atom and arene ligand.
680-688
Polynuclear Co(II) Myrtenates with 2,4-Lutidine
Abstract
The reaction of cobalt(II) chloride with potassium myrtenate (KMyr) followed by addition of 2,3-lutidine in ethanol gives the trinuclear compound [Co3(Myr)6(2,4-Lut)2] (I). The central cobalt(II) atom is linked to each of the two other metal atoms by three myrtenic acid anions. The reaction of a solution of compound I with lithium myrtenate (LiMyr) results in the formation of tetranuclear heterometallic complex [Li2-Co2(Myr)6(2,4-Lut)2] (II). Compound II is composed of two binuclear {LiCo(Myr)3(2,4-Lut)} moieties, in which the lithium(I) atoms are linked to cobalt(II) atoms by bridging myrtenate anions. The lithium atoms are connected by two oxygen atoms of acid anions. Compounds I and II were characterized by X-ray diffraction (CIF files CCDC nos. 1898096 (I), 1898097 (II)).
689-694
Principles of the Construction of Polymer Structures, Heteronuclear (13C, 15N) CP-MAS NMR, and Thermal Behavior of Heteroleptic Bismuth(III) Complexes of the General Composition [Bi(S2CNR2)2X] (X = NO3, Cl)
Abstract
The crystalline heteroleptic bismuth(III) complexes, [Bi{S2CN(iso-C4H9)2}2(NO3)] (I) and [Bi{S2CN(C3H7)2}2Cl] (II), are isolated in preparative yields. Both compounds form 1D polymer structures and are characterized by X-ray diffraction analysis (CIF files CCDC nos. 1877115 (I) and 1876364 (II)) and (13C, 15N) CP-MAS NMR spectroscopy. The coordination mode of each of the dialkyldithiocarbamate ligands is S,S′-anisobidentately terminal. The inorganic anions performing the μ2-bridging function participate in the binding of the adjacent metallic atoms to form zigzag polymer chains. A new mode of bismuth(III) binding involving all oxygen atoms (O,O'-anisobidentate coordination to each adjacent bismuth atom) is found for the bridging nitrate groups in compound I. The bismuth atoms in the studied compounds are characterized by the eightfold [BiS4O4] (I) or sixfold [BiS4Cl2] (II) environment. The thermal behavior of the synthesized complexes is characterized by the data of simultaneous thermal analysis, using parallel recording of thermogravimetry and differential scanning calorimetry curves. In both cases, Bi2S3 is the only final product of the thermal transformations of compounds I and II.
695-705
Metal Complexes with the N-Heterocyclic Ligand: Synthesis, Structures, and Thermal Decomposition
Abstract
The heterometallic nickel and iron chalcogenide complexes, (η5-C5H5)Ni(MeIm)S(µ2-SnPr)Mn(CO)2(η5-C5H5) (I) and (η5-C5H5)Fe(MeIm)(CO)(µ2-SPh)Mn(CO)2(η5-C5H5) (II), and the cobalt nitrosyl complex (MeIm)Co(NO)2I (IIIa, IIIb) (CIF files CCDC nos. 1911962 (I), 1911963 (II), 1911964 (IIIa), and 1911965 (IIIb)) are synthesized and structurally characterized. According to the data of thermogravimetry and differential scanning calorimetry (TG–DSC), the organic moiety of the molecule of complex I is lost to form the NiMnS residue, whereas ferrocene is formed upon the thermal decomposition of complex II.
706-711
Polynuclear Heteroligand Yb(III)–Er(III) Complexes as Potential Upconversion Materials
Abstract
The synthesis of complexes LnI(C6F5O)2 and LnCp(L)2 (Ln = Er, Yb; L = C6F5O, SONF), which are convenient precursors for the preparation of heteroligand bimetallic complexes, is described. The structures of YbI(C6F5O)2(DME)2 (I), CpEr(C6F5O)2(DME)[(C2H5)2O] (III), and CpYb(SONF)2(DME) (VI) were established by X-ray diffraction (CIF files CCDC (nos. 1902963 (I), 1902964 (III), and 1902965 (VI)). The developed methods were used to prepare heteroligand bimetallic Yb(III)–Er(III) complexes (C6F5O)2Yb[µ-(CF3)2CHO]2Er(C6F5O)2 and {(SONF)2Yb[µ-(CF3)2CHO]2-Er(SONF)2}x, which showed metal-centered emission inherent in Yb3+ and Er3+ ions λem = 985 and 1540 nm, respectively. This suggests that the obtained compounds can serve as promising upconversion materials.
712-720
Water-Soluble Chiral Y(III)–Cu(II) Metallamacrocyclic Phenylalaninehydroximate Complex
Abstract
A chiral Y(III)–Cu(II) metallamacrocyclic complex with L-phenylalaninehydroximate ligands was synthesized. The chirality of initial L-aminohydroximate ligands dictates the one-side orientation of the R-substituent relative to the internal O–Cu–N–O moiety. The molecular and electronic structures of the synthesized complex were studied by X-ray diffraction (CIF file CCDC no. 1903232) and quantum chemical calculations.
721-727
Cleavage of B−C bonds and Anion [PhBH3]− Formation in the Reaction of the Yb(II) Hydride Complex with BPh3
Abstract
The reaction of the amidinatehydride complex of divalent ytterbium [(Amd)YbII(μ2-H)]2 (Amd is {tert-BuC(NC6H3-iso-Pr2-2,6)2}) with BPh3 proceeds with the cleavage of the B−C bonds and affords the Yb(II)[(Amd)YbII(μ2-H3BPh)]2 complex containing the phenyltrihydroborate anion [PhBH3]−. The X-ray diffraction analysis (СIF file CCDC no. 1902290) shows that the [PhBH3]− anions in the complex are bridging. The “nonclassical” κ1-amido-η6-arene coordination mode to the Yb2+ ion is retained for the amidinate ligand.
728-733
Hydrogen Bonding Influenced Coordination Mode of Azide Ligand in Schiff base Copper(II) Complexes: Synthesis, Crystal Structures, and Antibacterial Activity
Abstract
Two copper(II) complexes, [CuL1N3] (I) and [CuL2(μ1, 1-N3)] (II), where L1 = 2-[(2-diethylaminoethylimino)methyl]-4,6-difluorophenolate, L2 = 2,4-difluoro-6-[(2-isopropylaminoethylimino)-methyl]phenolate, have been prepared and structurally characterized by elemental analyses, IR and UV-Vis spectra, as well as single crystal X-ray determination (CIF files CCDC nos. 1848289 (I) and 1848290 (II)). In complex I, the Cu atom is in square planar coordination, with the azide ligand in terminal coordination mode. In complex II, the Cu atom is in square pyramidal coordination, with the azide ligand in end-on bridging mode. The crystals are stabilized by hydrogen bonds, which influence the coordination mode of the azide ligand. The complexes have strong antibacterial activity against B. subtilis and S. aureus.
734-740
Novel Zn and Cd Coordination Polymers Assembled from Imidazole-based Zwitterionic Ligands: Synthesis, Crystal Structures, and Luminescence Properties
Abstract
Two transition-metal coordination polymers {[Zn2(L)2(HCOO)2]}n (I) and {[Cd2(L)3(HCOO)] ∙ 2H2O}n(II) (L = 1,3-bis(4-(methoxycarbonyl)benzyl)-1H-imidazol-3-ium anion) have been synthesized via solvo-thermal method. Both of the coordination polymers I and II were characterized by single-crystal X-ray diffraction (CIF files CCDC nos. 1834629 (I) and 1834630 (II)), FT-IR spectroscopy, elemental analysis and thermogravimetric analysis. The results shown compound I is a two dimensional sql layer structure containing interlocking structure between the left and right helix chains, and compound II is rare three dimensional six-fold interpenetrating dia topology framework. Luminescence investigations revealed that both of compound I and II emitted blue light.
741-747