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Vol 50, No 10 (2024)
Articles
Octahedral Halide Clusters of Niobium and Tantalum Bearing the Cluster Core {M6X12}
Abstract
Synthesis methods, molecular and electronic structures, and reactivity of the family of the octahedral clusters of niobium and tantalum halides bearing the {M6X12} cluster core are reviewed. Possible fields of the practical use of this class of compounds are considered.
629-647
Synthesis and Structure of Manganese Complexes with N,N’-bis[(2,4,6-trimethylphenyl)imino]acenaphthene
Abstract
Methods for the synthesis of new manganese(II) complexes with N,N’-bis[(2,4,6-trimethylphenyl) imino (acenaphthene (Tmp-bian), [Mn(Tmp-bian)Br2] (I), [Mn(Tmp-bian)(EtOH)Br2] (Ia), [Mn(Tmpbian) Cl2] (II), [Mn(Tmp-bian)2 (ClO4) 2] (III), and [Mn(Tmp-bian)2(OTs)2] (IV) were developed. The obtained compounds were characterized by elemental analysis and IR spectroscopy. The molecular structures of I, Iа, and III were determined by X-ray diffraction (CCDC no. 233510–233512). The electronic structures of I and III were established by quantum chemical calculations using density functional theory (DFT).
648-660
Adducts of Sterically Hindered Tellurium Catecholate with N-Methylpyrrolidone
Abstract
The formation of adducts of tellurium(IV) 3,6-di-tert-butyl catecholate (Te(Cat36)2) with N-methylpyrrolidone (NMP) is studied. The crystallization from a CH2Cl2–NMP–aromatic hydrocarbon mixture is found to result in the formation of dimeric complexes [{Te(Cat36)2}2(μ-NMP)(μ-arene)] (arene = C6H6, C7H8), whereas mononuclear [Te(Cat36)2(NMP)2] is formed from a CH2Cl2–NMP–alkane mixture. The formation of the adducts with aromatic hydrocarbons indicates a possibility of using the tellurium complexes for the separation of hydrocarbon mixtures, including an industrially important benzene–cyclohexane mixture.
661-668
Ditopic Centrosymmetric Mercaptobenzothiazole Dilithium Salts: From the Molecular Complex to Luminescent 1D Metal-Organic Frameworks
Abstract
The reaction of lithium amide LiN(Si(Me)3)2 and ditopic heterocyclic ligand benzo[1,2-d:4,5-d′]bis(thiazole)-2,6(3H,7H)-dithione (H2L) in dimethoxyethane (DME) affords the binuclear molecular complex Li2L(DME)4 (I). New compounds [[Li2L(ДМСО)4 • (ДМСО)2]n (II) and [Li2L(ДМСО)4 • (ТГФ)2]n (III) are prepared by the recrystallization of compound I using a DMSO–diethyl ether or DMSO/THF mixture of solvents, respectively. According to the XRD data, these compounds are one-dimensional metalorganic frameworks (MOFs) differed by the arrangement of the bis(thiazole) fragments relative to each other and the Li2O2 fragment in the polymer chain, which affects the luminescence properties. The molecular structures of compounds I–III are determined by XRD (CIF files CCDC nos. 2334192 (I), 2334193 (II), and 2334194 (III)).
669-678
Characteristic Features of the Synthesis of 2,1,3-Benzothiadiazole-Substituted 1,3-Iminophosphine and Platinum Complex of this Compound
Abstract
In an attempt to synthesize a new iminomethylphosphine, tBuC(Ph2P)=N-Btd (Btd = 2,1,3-benzothiadiazole) by a three-step procedure including (1) NH2-Btd + tBuC(=O)Cl → tBuC(=O)NH-Btd; (2) tBuC(=O)NH-Btd + SOCl2 → tBuC(Cl)=N-Btd; (3) tBuC(Cl)=N-Btd + Ph2PSiMe3 → tBuC(Ph2P)=N-Btd, it was found that the second step is accompanied by the chlorination of the carbocycle in the benzothiadiazole moiety. The reaction of the imidoyl chloride tBuC(Cl)=N-(7-Cl-Btd) formed in this reaction with Ph2PSiMe3 gave 1,3-iminomethylphosphine tBuC(Ph2P)=N-(7-Cl-Btd) (PC=N). The byproducts formed in this step include 1,3-aminomethylphosphine oxide tBuC{Ph2P(O)}NH-(7-Cl-Btd) (POCN) and (Ph2POx)2,, resulting from partial oxidation and hydrolysis. The reactions of PC=N and POCN with [Pt(COD)Cl2] (COD = 1.3-cyclooctadiene) were studied. In the case of PC=N, the reaction affords the [Pt(PC=N)2Cl2] complex. In the latter case, cleavage of the P–C bond in POCN takes place, and [PtCl2(Ph2POH)2](POCN) and [Pt(CH3CN){tBuC-NH-(7-Cl-Btd)}Cl]. are isolated from the reaction mixture. The structures of the new compounds were established by single-crystal X-ray diffraction (tBuC(Cl)N-(7-Cl-Btd)), 2335152 (POCN · Et2O), 2335149 (Ph2POx)2, 2335153 ([Pt(PC=N)2Cl2]), 2335154 ([PtCl2(Ph2POH)2](POCN)), 2335151 ([Pt(CH3CN)(tBuC-NH-(7-Cl-Вbtd))Cl]).
679-692
Compounds of s-Metals with Spin-Labeled Nitrophenol
Abstract
A series of paramagnetic salts of s-elements (Li, Na, K, Rb, Cs) with deprotonated nitroxide radical, 2-(2-hydroxy-5-nitrophenyl)-4,4,5,5-tetramethyl-4,5-dihydro-1H-imidazol-1-oxyl 3-oxide (L), were synthesized and isolated as crystals. According to X-ray diffraction data, these compounds are polymers of different dimensionality (CCDC nos. 2342497–2342506). As indicated by the results of quantum chemical calculations and magnetic measurements, weak antiferromagnetic exchange interactions predominate in the paramagnetic salts, with the interaction energy decreasing with increasing radius of the alkali metal ion.
693-707
Layered Coordination Polymers Based on the Cluster Complexes [Re6Q8(CN)6]4– (Q = S or Se) and Dimeric Cations {(Ag(Dppe))2(μ-Dppe)}2+
Abstract
The reactions of salts of cluster anions [Re6Q8(CN)6]4– with the [Ag(CN)2]– dicyanoargentate anion in the presence of 1,2-bis(diphenylphosphino)ethane are studied. Two new coordination polymers, [{(Ag(Dppe))2 (µ-Dppe)}2{Re6S8(CN)6}]⋅H2O (I) and [{(Ag(Dppe))2(µ-Dppe)}2{Re6Se8(CN)6}]0,85[{(Ag(Dppe))(Ag(DppeSe))(µ-Dppe)}2{Re6Se8(CN)6}]0,15 (II), are prepared by the solvothermal synthesis. The XRD study of single crystals of the compounds (CIF files CCDC nos. 2341356 (I) and 2341355 (II)) shows their layered structures. The XRD study of crystalline powders of the compounds shows that the synthesis of compound II leads to the formation of two crystalline phases, one of which is isostructural to compound I. The luminescence parameters of the solid-state compounds (quantum yields, emission lifetimes) resemble the parameters of other coordination polymers based on the [Re6Q8(CN)6]4– ions.
708-721
Lanthanide(III) Complexes Based on Tris(2-pyridyl)phosphine Oxide: First Examples
Abstract
A series of mononuclear complexes [Ln(Py3PO)2(NO3)3] · 1.5Me2CO (Ln = Sm, Eu, Gd, Tb, Dy) and [Ln(Py3PO)(TTA)3] (Ln = Eu, Tb; TTA‒ is thenoyltrifluoroacetonate ion) based on tris(2-pyridyl) phosphine oxide (Py3PO) is synthesized and studied. In the synthesized compounds, Py3PO acts as the N,O-chelate ligand resulting in the formation of coordination polyhedra N2O8 and NO7 of the Ln atom in complexes [Ln(Py3PO)2(NO3)3] · 1.5Me2CO and [Ln(Py3PO)(TTA)3], respectively. The complexes of Sm3+, Eu3+, Tb3+ and Dy3+ ions exhibit lanthanide-centered photoluminescence in the solid phase at 300 K. The energy of the T1 triplet level of Py3PO is determined to be 21 900 cm‒1 from the ligand-centered phosphorescence spectrum of the Gd(III) complex at 77 K. Among the complexes with the NO3‒ ions, Py3PO exhibits the highest sensibilizing ability toward Tb3+, whereas the ligand environment in the complexes with the TTA‒ ions most efficiently sensibilizes the Eu3+ ion luminescence.
722-736