Formation, Characterization, and Bonding of - and -[PtCl{Te(CH)}], -[PtCl{Te(CH)}], and --[PtCl{Te(CH)}]: Experimental and DFT Study.

[PtCl{Te(CH)}] () was synthesized from the cyclic telluroether Te(CH) and -[PtCl(NCPh)] in dichloromethane at room temperature under the exclusion of light. The crystal structure determination showed that in the solid state, crystallizes as yellow plate-like crystals of the -isomer and the orange-red interwoven needles of . The crystals could be separated under the microscope.

Experimental and computational investigation on the formation pathway of [RuCl(CO)(ERR')] (E = S, Se, Te; R, R' = Me, Ph) from [RuCl(CO)] and ERR'.

The pathways to the formation of the series of [RuCl(CO)(ERR')] (E = S, Se, Te; R, R' = Me, Ph) complexes from [RuCl(CO)] and ERR' have been explored experimentally in THF and CHCl, and computationally by PBE0-D3/def2-TZVP calculations. The end-products and some reaction intermediates have been isolated and identified by NMR spectroscopy, and their crystal structures have been determined by X-ray diffraction. The relative stabilities of the [RuCl(CO)(ERR')] isomers follow the order > > > ≈ (the terms / refer to / arrangement of the ligands in the order of Cl, CO, and ERR').

Correction: Tellurium: a maverick among the chalcogens.

Correction for 'Tellurium: a maverick among the chalcogens' by Tristram Chivers and Risto S. Laitinen, Chem. Soc.

Chalcogen-Bonding Interactions in Telluroether Heterocycles [Te(CH ) ] (n=1-4; m=3-7).

Invited for the cover of this issue are the groups of Risto Laitinen at University of Oulu and Wolfgang Weigand at Friedrich Schiller University Jena. The image depicts a picturesque view of the Te⋅⋅⋅Te close contacts forming infinite tubular shafts in 1,9,17,25-Te (CH ) . The cover artwork was designed and created by Marko Rodewald.

Iron-Intercalated Zirconium Diselenide Thin Films from the Low-Pressure Chemical Vapor Deposition of [Fe(η-CHSe)Zr(η-CH)].

Transition metal chalcogenide thin films of the type Fe ZrSe have applications in electronic devices, but their use is limited by current synthetic techniques. Here, we demonstrate the synthesis and characterization of Fe-intercalated ZrSe thin films on quartz substrates using the low-pressure chemical vapor deposition of the single-source precursor [Fe(η-CHSe)Zr(η-CH)]. Powder X-ray diffraction of the film scraping and subsequent Rietveld refinement of the data showed the successful synthesis of the FeZrSe phase, along with secondary phases of FeSe and ZrO.

Chalcogen-Bonding Interactions in Telluroether Heterocycles [Te(CH ) ] (n=1-4; m=3-7).

The Te⋅⋅⋅Te secondary bonding interactions (SBIs) in solid cyclic telluroethers were explored by preparing and structurally characterizing a series of [Te(CH ) ] (n=1-4; m=3-7) species. The SBIs in 1,7-Te (CH ) , 1,8-Te (CH ) , 1,5,9-Te (CH ) , 1,8,15-Te (CH ) , 1,7,13,19-Te (CH ) , 1,8,15,22-Te (CH ) and 1,9,17,25-Te (CH ) lead to tubular packing of the molecules, as has been observed previously for related thio- and selenoether rings. The nature of the intermolecular interactions was explored by solid-state PBE0-D3/pob-TZVP calculations involving periodic boundary conditions.

Neutral binary chalcogen-nitrogen and ternary S,N,P molecules: new structures, bonding insights and potential applications.

Early theoretical and experimental investigations of inorganic sulfur-nitrogen compounds were dominated by (a) assessments of the purported aromatic character of cyclic, binary S,N molecules and ions, (b) the unpredictable reactions of the fascinating cage compound S4N4, and (c) the unique structure and properties of the conducting polymer (SN)x. In the last few years, in addition to unexpected developments in the chemistry of well-known sulfur nitrides, the emphasis of these studies has changed to include nitrogen-rich species formed under high pressures, as well as the selenium analogues of well-known S,N compounds. Novel applications have been established or predicted for many binary S/Se,N molecules, including their use for fingerprint detection, in optoelectronic devices, as high energy-density compounds or as hydrogen-storage materials.

Titanocene Selenide Sulfides Revisited: Formation, Stabilities, and NMR Spectroscopic Properties.

[TiCp₂S₅] (phase ), [TiCp₂Se₅] (phase ), and five solid solutions of mixed titanocene selenide sulfides [TiCp₂SeS₅] (Cp = C₅H₅) with the initial Se:S ranging from 1:4 to 4:1 (phases ⁻) were prepared by reduction of elemental sulfur or selenium or their mixtures by lithium triethylhydridoborate in thf followed by the treatment with titanocene dichloride [TiCp₂Cl₂]. Their Se and C NMR spectra were recorded from the CS₂ solution. The definite assignment of the Se NMR spectra was based on the PBE0/def2-TZVPP calculations of the Se chemical shifts and is supported by C NMR spectra of the samples.

Accessing new 2D semiconductors with optical band gap: synthesis of iron-intercalated titanium diselenide thin films LPCVD.

Fe-doped TiSe thin-films were synthesized low pressure chemical vapor deposition (LPCVD) of a single source precursor: [Fe(η-CHSe)Ti(η-CH)] (1). Samples were heated at 1000 °C for 1-18 h and cooled to room temperature following two different protocols, which promoted the formation of different phases. The resulting films were analyzed by grazing incidence X-ray diffraction (GIXRD), X-ray photoelectron spectroscopy (XPS), scanning electron microscope (SEM) and UV/vis spectroscopy.

Macrocycles containing 1,1'-ferrocenyldiselenolato ligands on group 4 metallocenes.

Macrocyclic [Fe(η5-C5H4Se)2M(η5-C5H4R)2]2 [M = Ti (1), Zr (2), Hf (3), R = H; and M = Zr (4), Hf (5), R = tBu] were prepared and characterized by 77Se NMR spectroscopy and the crystal structures of 1-3 and 5 were determined by single-crystal X-ray diffraction. The crystal structure of 4 is known and the complex is isomorphous with 5. 1-5 form mutually similar macrocyclic tetranuclear complexes in which the alternating Fe(C5H4Se)2 and M(C5H4R)2 centers are linked by selenium bridges.

Fundamental chemistry of binary S,N and ternary S,N,O anions: analogues of sulfur oxides and N,O anions.

Binary S,N anions, e.g., NSN and SSNSS, and related ternary S,N,O anions such as the structural isomers NSO/SNO and SSNO are rarely mentioned in inorganic chemistry textbooks, despite the fact that their salts were synthesised and structurally characterised more than 30 years ago.

Clathrate Structure Determination by Combining Crystal Structure Prediction with Computational and Experimental Xe NMR Spectroscopy.

An approach is presented for the structure determination of clathrates using NMR spectroscopy of enclathrated xenon to select from a set of predicted crystal structures. Crystal structure prediction methods have been used to generate an ensemble of putative structures of o- and m-fluorophenol, whose previously unknown clathrate structures have been studied by Xe NMR spectroscopy. The high sensitivity of the Xe chemical shift tensor to the chemical environment and shape of the crystalline cavity makes it ideal as a probe for porous materials.

Insights into the formation of inorganic heterocycles via cyclocondensation of primary amines with group 15 and 16 halides.

Cyclocondensation is a major preparative route for the generation of inorganic heterocycles especially in the case of ring systems involving a Group 15 or 16 element linked to nitrogen. This Perspective will consider recent experimental and computational studies involving the reactions of primary amines (or their synthetic equivalents) with pnictogen and chalcogen halides. The major focus will be a discussion of the identity and role of acyclic intermediates in the reaction pathways to ring formation, as well as the nature of the heterocycles so formed.

DFT calculations in the assignment of solid-state NMR and crystal structure elucidation of a lanthanum(iii) complex with dithiocarbamate and phenanthroline.

The molecular, crystal, and electronic structures as well as spectroscopic properties of a mononuclear heteroleptic lanthanum(iii) complex with diethyldithiocarbamate and 1,10-phenanthroline ligands (3 : 1) were studied by solid-state C and N cross-polarisation (CP) magic-angle-spinning (MAS) NMR, X-ray diffraction (XRD), and first principles density functional theory (DFT) calculations. A substantially different powder XRD pattern and C and N CP-MAS NMR spectra indicated that the title compound is not isostructural to the previously reported analogous rare earth complexes with the space group P2/n. Both C and N CP-MAS NMR revealed the presence of six structurally different dithiocarbamate groups in the asymmetric unit cell, implying a non-centrosymmetric packing arrangement of molecules.

Synthesis, characterization, and ligand behaviour of a new ditelluroether (CH)Te(CH)Te(CH) and the concurrently formed ionic [(CH)Te(CH)]Br.

The reaction of 1-naphthyl bromide with n-butyl lithium, elemental tellurium, and 1,4-dibromobutane in THF affords both (CH)Te(CH)Te(CH) (1) and [(CH)Te(CH)]Br (2) in good yields. 1 is preferentially formed at low temperatures and is a rare example of a structurally characterized ditelluroether in which the tellurium atoms are bridged by a hydrocarbon chain. In the solid state, 1 shows secondary bonding TeTe interactions, which connect the molecules into layers which are further linked to 3-dimensional frameworks by TeH hydrogen bonds.

Theoretical and Synthetic Study on the Existence, Structures, and Bonding of the Halide-Bridged [B2X7](-) (X = F, Cl, Br, I) Anions.

While hydrogen bridging is very common in boron chemistry, halogen bridging is rather rare. The simplest halogen-bridged boron compounds are the [B2X7](-) anions (X = F, Cl, Br, I), of which only [B2F7](-) has been reported to exist experimentally. In this paper a detailed theoretical and synthetic study on the [B2X7](-) anions is presented.

The role of imidoselenium(II) chlorides in the formation of cyclic selenium imides via cyclocondensation.

The third member of the series of imidoselenium(II) chlorides ClSe[N(tBu)Se]nCl (n = 3) (9) has been isolated from the cyclocondensation reaction of tBuNH2 and SeCl2 in THF in a molar ratio of ca. 3:1 and characterized in the form of two polymorphs 9a and 9b by single crystal X-ray analysis. The unusual structural features of this nine-atom chain are explained satisfactorily in terms of a bonding model that invokes intra-molecular secondary bonding interactions and hyperconjugation.

Mercury- and cadmium-assisted [2 + 2] cyclodimerization of tert-butylselenium diimide.

The complexes [MCl2{N,N'-(t)BuNSe(μ-N(t)Bu)2SeN(t)Bu}] [M = Cd (1), Hg (2)] were obtained in high yields by the reaction of tert-butylselenium diimide Se(IV)(N(t)Bu)2 with CdCl2 or HgCl2 in tetrahydrofuran. Recrystallization of 1 and 2 from acetonitrile (MeCN) afforded yellow crystals of 1·MeCN and 2·MeCN, respectively. Isomorphic 1·MeCN and 2·MeCN contain an unprecedented dimeric selenium diimide ligand, which is N,N'-chelated to the metal through exocyclic imido groups.

Experimental and Computational (77)Se NMR Investigations of the Cyclic Eight-Membered Selenium Imides 1,3,5,7-Se4(NR)4 (R = Me, (t)Bu) and 1,5-Se6(NMe)2.

The cyclocondensation reaction of equimolar amounts of SeCl2 and (Me3Si)2NMe in THF affords 1,3,5,7-Se4(NMe)4 (5b) [δ((77)Se) = 1585 ppm] in excellent yield. An X-ray structural determination showed that 5b consists of cyclic, puckered crown-shaped molecules with a mean Se-N bond length of 1.841 Å typical of single bonds.

Tellurium: a maverick among the chalcogens.

The scant attention paid to tellurium in both inorganic and organic chemistry textbooks may reflect, in part, the very low natural abundance of the element. Such treatments commonly imply that the structures and reactivities of tellurium compounds can be extrapolated from the behaviour of their lighter chalcogen analogues (sulfur and selenium). In fact, recent findings and well-established observations clearly illustrate that this assumption is not valid.

Crystal structure of bis-[(5-oxo-oxolan-3-yl)triphen-ylphosphanium] hexa-iodido-tellurate(IV).

The asymmetric unit of the title salt, [C22H20O2P]2 (+)[TeI6](2-), consists of one triphenyl(5-oxooxolan-3-yl)phosphanium cation and one half of a hexa-iodido-tellurate(IV) dianion. The Te atom is located at an inversion centre and is octa-hedrally coordinated by six I atoms. The Te-I bond lengths range from 2.

Crystal structure of tris-(phenyl-seleno-lato-κSe)tris-(tetra-hydro-furan-κO)thulium(III).

In the title compound, [Tm(C6H5Se)3(C4H8O)3], the Tm(III) atom lies on a threefold rotation axis and is coordinated by three phenyl-seleno-late ligands and three tetra-hydro-furan ligands leading to a distorted fac-octa-hedral coordination environment. The Tm-Se and Tm-O bond lengths are 2.7692 (17) and 2.

Crystal structure of bis-{μ-2-[(di-methyl-amino)-meth-yl]ferrocene-seleno-lato}bis[chlorido-palladium(II)].

The dinuclear title compound, [PdCl{Se[(C5H5)Fe(C5H3)2CH2N(CH3)2]}]2 was obtained by the reaction of [PdCl2(NCPh)2] with 2-[(N,N'-di-methyl-amino)-meth-yl]ferro-cene-seleno-late and the crystals for the structure determination were grown from a mixture of THF and n-hexane. Both Pd(II) atoms are coordinated by the bridging Se atoms and by the amino N atoms of the bidentate 2-[(N,N'-di-methyl-amino)-meth-yl]ferrocene-seleno-late ligand, as well as by Cl atoms, and show a distorted square-planar coordination. The angle between the Pd-Se-Se planes of the two Pd atoms is 149.

Chlorido-{2-[(di-methyl-amino)-meth-yl]benzene-seleno-lato-κ(2) N,Se}(tri-phenyl-phosphane-κP)palladium(II).

The asymmetric unit of the title compound, [PdCl(C9H12NSe)(C18H15P)], contains two independent mol-ecules. In both cases, the Pd(2+) cations are coordinated by the Se and N atoms of the chelating bidentate 2-[(di-methyl-amino)-meth-yl]benzene-seleno-late ligand. The chloride ligand lies trans to selenium and the tri-phenyl-phosphane ligand is trans to nitro-gen.

1,1'-(Diselanediylbis{[P,P-diphenyl-N-(tri-methyl-sil-yl)phospho-rimido-yl]methanylyl-idene})bis-[1,1-diphenyl-N-(tri-methyl-sil-yl)-λ(5)-phosphanamine] pentane disolvate.

The title compound, C62H78N4P4Se2Si4·2C5H12, is made up of two [SeC(PPh2NSiMe3)(PPh2NHSiMe3)] units related by an inversion center situated at the mid-point of the diselenide bond. It crystallized with two disordered mol-ecules of pentane used as solvent of crystallization. It is a rare example of an anti-periplanar diselenide and exhibits a long Se-Se bond of 2.