0000000001304595
AUTHOR
Volodymyr Olijnyk
Bridging vs. Chelating Coordination Modes of Vinylsilanes in CuIπ-Complexes: Structure and Stability
Two new copper(I) olefin complexes, [Cu6Cl6(MTrVS)2] (1) and [Cu2Cl2(DMVSP)2] (2), of tridentate bridging methyltrivinylsilane (MTrVS) and bidentate chelating 2-[dimethyl(vinyl)silyl]pyridine (DMVSP) have been synthesized and characterized by single-crystal X-ray structure analysis, IR and 1H NMR spectroscopy. It has been shown that using the alkenylsilanes with required electronic properties, molecular symmetry and conformational flexibility, it is possible to control the formation of optimal copper(I) halide oligomers. The obtained results, together with relevant literature data, also illustrate how the coordination mode of vinylsilanes is related to Cu–(C=C) bond strengthening and, conse…
A new copper(II) chelate complex with tridentate ligand: Synthesis, crystal and molecular electronic structure of aqua-(diethylenetriamine-N, N′, N′′)-copper(II) sulfate monohydrate and its fire retardant properties
Abstract The crystals of a new aqua-(diethylenetriamine-N, N′, N′′)-copper(II) sulfate monohydrate have been synthesized by direct interaction of solid copper(II) sulfate pentahydrate with diethylenetriamine (deta). The crystal structure of [Cu(deta)H2O]SO4⋅H2O (1) has been determined by X-ray diffraction methods at 100 K and characterized using X-ray powder diffraction pattern: space group P 1 ¯ , a = 7.2819(4), b = 8.4669(4), c = 8.7020(3) A, α = 83.590(3), β = 89.620(4), γ = 84.946(4)°, Z = 2. The environment of the Cu(II) atom is a distorted, elongated square pyramid which consists of three nitrogen atoms of the deta molecule and oxygen atom of the water molecule in the basal plane of t…
Poly[μ2-chloro-μ2-1,4-oxathiane-κ2S:S-copper(I)]
The title complex, [CuCl(C4H8OS)]n, contains infinite spiral (CuS)n chains linked by bridging Cl atoms into layers. The Cl atoms do not form polymeric fragments with CuI, but combine into isolated centrosymmetric Cu2Cl2 units. The compound is non-isomorphous with the Br-containing analogue, which contains Cu8S8 rings linked by Br atoms into chains. The O atom of the 1,4-oxathiane molecule does not realize its coordination abilities in the known copper(I)-halide complexes, while in copper(II)-halide complexes, oxathiane is coordinated via the S and O atoms. This falls into a pattern of the preferred interactions, viz. weak acid (CuI atom) with weak base (S atom) and harder acid (CuII atom)…
Coordination environment friendly silicon in copper(I) chloride π-complexes with tetravinylsilane and dimethyltetravinyldisiloxane
Abstract Two crystal complexes of copper(I) chloride with tetravinylsilane (TVS) dimethyltetravinyldisiloxane (DMTVDS) were prepared and examined by IR spectroscopy and X-ray diffraction: sp. gr. P2/a, Z = 4, a = 13.428(1) A, b = 7.9584(7) A, c = 14.694(1) A for [Cu4Cl4(TVS)]; sp. gr. P21/c, a = 10.505(1) A, b = 13.487(1) A, c = 13.870(1) A for [Cu4Cl4(DMTVDS)]. The influence of the vinylsilicon ligands on the efficiency of the Cu⋯C C interaction is discussed. Thus, the consideration of dSi ← π∗C C ← dCu conjugate system may help to understand how the silicon π-acceptor properties influence on the degree of trigonal distortion of the Cu(I) coordination tetrahedron as well as on the inorgani…
Copper‐Promoted Formation of Vinylsiloxanes
The metathesis reactions of chlorovinylsilanes with copper(I) oxide are reported. The process is catalyzed by HCl which can be in situ generated via hydrolysis of chlorosilanes by traces of water present in the system. An appearance of olefin/CuCl π‐intermediates can provide a stereoselectivity of the process and alter the pathway of siloxanes formation employing Cu2O as the source of oxygen. It was also shown that acetonitrile may be available as a solvent for construction of the systems with large preparative capabilities, including those based on the use atmospheric oxygen in siloxane synthesis.
The first silver(I) nitrate π-complexes with unsaturated organosilicons: Synthesis and structural characterization of [Ag(DADPS)xNO3] (DADPS=diallyldiphenylsilane, x=0.75; 1)
Abstract Tetraethylene glycol dimethyl ether (tetraglyme) was used for the first time to induce the activation of silver nitrate resulting in the step-by-step formation of complexes with diallyldiphenylsilane (DADPS). Two crystal compounds of this series were examined by FTIR spectroscopy and X-ray diffraction. The analysis of the obtained data showed that the Ag (C C) η 2 -interaction is involved in the synergistic effect of intra and intermolecular forces. In particular the interlayer π–π stacking interactions promoted by asymmetric weak Ag C(phenyl) bond have a significant influence on the thermal behavior and stability of the synthesized products. It was also found that a decrease of si…
Tetraallylsilane π-Complexation: Synthesis and Structure of [Cu5Cl5(CH2-CH=CH2)4Si]
By alternating-current electrochemical technique, starting from CuCl2·2H2O and tetraallylsilane (TAS), crystals of the π complex [Cu5Cl5(CH2–CH=CH2)4Si] (I) were obtained, FTIR characterized and structurally investigated. The structure of I is monoclinic, space group P21/n, a = 12.292(3), b = 12.083(3), c = 13.356(3) A, β = 90.19(3)°, V = 1983.7(9) A3 [at 100(2) K], Z = 4; R1 = 0.0379, wR2 = 0.1040 for 3583 reflections. The TAS molecule behaves as a tetradentate cross-bridged ligand linking four (Cu5Cl5)∞ fragments through the C=C bonds. The influence of the inorganic part and ligand symmetries combined with their conformational abilities on the overall crystal symmetry is discussed.
Synthesis, structural, and thermal characterization of a new binuclear copper(II) chelate complex bearing an amine-hardener for epoxy resins
A new di(μ-carbonato)bis[aqua(diethylenetriamine)copper(II)] hexahydrate complex, [{Cu(NH(C2H4NH2)2)(H2O)(μ-CO3)}2]⋅6H2O (1), was synthesized by direct interaction of malachite with diethylenetriamine (dien). The crystals of 1 were characterized by X-ray powder diffraction and IR spectra, as well as structurally characterized. Compound 1 consists of [{Cu(dien)(H2O)(μ-CO3)}2] discrete units whose CO32– anions play the role of bridging ligands combining two Cu(II) chelate cores into a centrosymmetric dimer. The elongated octahedral environment of Cu2+ consists of three nitrogens of dien and an oxygen from CO32– at the base of the bipyramid; the two apical positions of such polyhedron are occu…
Synthesis, crystal and molecular-electronic structure, and kinetic investigation of two new sterically hindered isomeric forms of the dimethyl[methyl(phenylsulfonyl)amino]benzenesulfonyl chloride
Two new structural isomers – 2,4-dimethyl-5-[methyl(phenylsulfonyl)amino]benzenesulfonyl chloride (1) and 2,4-dimethyl-3-[methyl(phenylsulfonyl)amino]benzenesulfonyl chloride (2) were synthesized by interaction of N-(2,4-dimethylphenyl)-N-methyl-benzenesulfonamide or N-(2,6-dimethylphenyl)-N-methylbenzenesulfonamide with chlorosulfonic acid. Both compounds have been structurally characterized by X-ray single crystal diffraction at 100 K. The crystals of 1 are triclinic: space group View the MathML source, a = 8.1542(2), b = 11.0728(3), c = 11.2680(3) Å, α = 116.557(3), β = 95.155(2), γ = 108.258(2)°, V = 831.97(4) Å3, Z = 2, R = 0.0251 for 2429 reflections; the crystals of 2 are monoclinic:…
Spectral and structural insights of copper reduction pathways in the system of CuX2-R2S (X=Cl, Br; R=allyl, n-propyl)
Abstract We have explored the behaviour of Cu(II)/Cu(I) redox couple in the system CuX2-R2S, X = Cl, Br; R = allyl, n-propyl, under anhydrous and anaerobic conditions, thus simulating the reduction half cycle in the copper catalyzed oxidation of thioethers. In doing so, the Cl−Br substitution was critical for tuning the reduction potentials, while the replacement of propyl group by allyl group supported the trapping of oxidation by-product, halogen molecules. It was therefore possible to use the spectrophotometric titration, thereby providing information on the distribution of complex species in acetonitrile solution. The study showed that the trinuclear mixed−valence copper (I-II-II) aggre…
Crystal polymorphism of (μ4–O)-body centered adamantanoid Cu(II) complexes
Abstract Two novel polymorphs of [Cu4(μ4–O)(μ–Cl)6(DASO)4], (DASO = diallyl sulfoxide; C6H10OS), rhombic (C) and triclinic (D), were obtained and examined by single crystal X-ray diffraction analysis at two temperatures, 295(2) and 100(1) K. This study, in addition to our recent work on the tetragonal (A) and trigonal (B) forms of the title compound, allowed determining the nature of polymorphism and temperature-induced phase transitions. It is stated that both the packing arrangement and the displacive transformation integrate these structures, forming the symmetrically and thermodynamically related series: A,B → C → D. The C3h → C4 distortion of Cu(II) trigonal bipyramidal coordination ge…
A new copper(II) chelate complex with polyamines as fire retardant and epoxy hardener: Synthesis, crystal and electronic structure, and thermal behavior of (ethylenediamine-N,N′)-(diethylenetriamine-N,N′,N″)-copper(II) hexafluoridosilicate
A new (ethylenediamine-N,N′)-(diethylenetriamine-N,N′,N″)-copper(II) hexafluoridosilicate complex, [Cu(eda)(deta)]SiF6 (1) (eda – ethylenediamine; deta – diethylenetriamine), was synthesized by direct interaction of anhydrous CuSiF6 with polyethylenepolyamine (pepa – H2N[C2H4NH]nH, where n = 1 (eda) and 2 (deta)). The crystals of 1 were characterized by IR spectroscopy and X-ray diffraction. Compound 1 consists of SiF62− discrete anions and [Cu(eda)(deta)]2+ complex cations whose Cu2+ ions are chelated by eda and deta. The coordination polyhedron of Cu(II) atom is an elongated square pyramid which consists of four nitrogen atoms belonging to NH2 groups of eda and NH2 and NH groups of …
Polymorphism of Copper(I) Halide π-Complexes: Synthesis and Structure of a New Modification of [Cu2Cl2(CH2=CH–CH2)2O]
A new polymorph of [Cu2Cl2(CH2=CH-CH 2)2O] has been obtained by an alternating-current electrochemical synthesis starting from CuCl2 and triallylphosphite. Diallylether was obtained in statu nascendi via transetherification of triallylphosphite. The structure is monoclinic, space group P21/n, a = 7.6738(7), b = 6.5128(4), c = 18.2689(18) A, β = 91.644(11)°, V = 912.67(13) A3 (at 150 K), Z = 4; R1 = 0.0339, wR2 = 0.0822. Flexibility of the organic ligand and weak interactions copper⋯halogen have been identified as the main reasons enabling polymorphism in molecular π-complexes of copper(I). ©2008 Wiley-VCH Verlag GmbH & Co. KGaA.
Crystal structures of allyltriphenyl-phosphonium halogenocuprates(I)
Alternating-current electrochemical synthesis is used to obtain for the first time halogenocuprates of an allyl derivative of phosphonium of the composition (CH2=CHCH2(C6H5)3P)CuX2 (X = Br (I), Cl (II)). Compound I crystallizes in the space group P21, a = 9.6341(3) A, b = 12.4167(4) A, c = 9.9618(4) A, β = 117.484(5)°, Z = 2. Compound II crystallizes in the space group P21/n, a = 9.9725(5) A, b = 15.4586(8) A, c = 13.7557(5) A, β = 90.429(4)°, Z = 4. In the structures of I and II quasilinear CuX 2 − anions are held by C-H…X hydrogen bonds inside a framework formed by the stacking of phenyl groups from CH2=CHCH2(C6P5)3P+ cations. Allyl groups are not involved in coordination with copper(I) a…
A crucial role of adamantanoid Cu(II) complexes in the redox systems: CuCl–diallylsulfoxide–O2 and CuCl2–diallylsulfide–O2
Abstract The hypothetically reversible [Cu(I)(diallylsulfoxide)] ↔ O 2 [Cu(II)(diallylsulfide)] system was examined by FTIR spectroscopy and X-ray diffraction. It is stated that the Cu4OCl6 body centered adamantanoid cages, appearing at both the substrate and product sites, act as a template to promote the oxidation of diallylsulfide to diallylsulfoxide or Cu(I) to Cu(II), thus making the reaction irreversible. Each of these two adamantanoid cores possesses a different point symmetry as well as self assembly mode to form two polymorphs of the [Cu4OCl6(diallylsulfoxide)4] complex. Their polymorphic relationships based on the symmetry homology S4 ← Td → C3, as well as the distortion in the Cu…
CCDC 1962246: Experimental Crystal Structure Determination
Related Article: Marietta Białoń, Błażej Dziuk, Volodymyr Olijnyk|2020|Eur.J.Inorg.Chem.|2020|1790|doi:10.1002/ejic.202000134
CCDC 1962243: Experimental Crystal Structure Determination
Related Article: Marietta Białoń, Błażej Dziuk, Volodymyr Olijnyk|2020|Eur.J.Inorg.Chem.|2020|1790|doi:10.1002/ejic.202000134
CCDC 1962245: Experimental Crystal Structure Determination
Related Article: Marietta Białoń, Błażej Dziuk, Volodymyr Olijnyk|2020|Eur.J.Inorg.Chem.|2020|1790|doi:10.1002/ejic.202000134
CCDC 1831147: Experimental Crystal Structure Determination
Related Article: Helen Lavrenyuk, Borys Mykhalichko, Błażej Dziuk, Volodymyr Olijnyk, Oleg Mykhalichko|2018|Arab.J.Chem.|13|3060|doi:10.1016/j.arabjc.2018.08.014
CCDC 1962244: Experimental Crystal Structure Determination
Related Article: Marietta Białoń, Błażej Dziuk, Volodymyr Olijnyk|2020|Eur.J.Inorg.Chem.|2020|1790|doi:10.1002/ejic.202000134