A novel rhenium(III) complex with bis(pyrazol-1-yl)methane: X-ray structure and DFT calculations for [ReCl3(bpzm)(PPh3)]

The [ReCl₃(MeCN)(PPh₃)₂] complex reacts with bis(pyrazol-1-yl)methane (bpzm) to give [ReCl₃(bpzm)(PPh₃)]. This compound has been studied by IR, UV–Vis spectroscopy, magnetic measurement and X-ray crystallography. The molecular orbital diagram of [ReCl₃(bpzm)(PPh₃)] has been calculated with the density functional theory (DFT) method. The spin-allowed triplet–triplet electronic transitions of [ReCl₃(bpzm)(PPh₃)] have been calculated with the time-dependent DFT method, and the UV–Vis spectrum of the title compound has been discussed on this basis. The magnetic behavior is characteristic of a mononuclear d⁴ low-spin octahedral Re(III) complex (³T_1g ground state) and arises because of the large spin–orbit coupling (ζ = 2500 cm⁻¹), which gives a diamagnetic ground state.     

Synthesis,spectroscopic characterization,X-ray structure and DFT calculations of rhenium(III) complex with 1-isoquinolinyl phenyl ketone

The [ReCl₃(MeCN)(PPh₃)] complex reacts with 1-isoquinolinyl phenyl ketone (N–O) to give [ReCl₃(N–O)(PPh₃)]. The compound has been studied by IR, UV–Vis spectroscopy, magnetic measurements and X-ray crystallography. The magnetic behavior is characteristic of mononuclear octahedral Re(III) complex with d⁴ low-spin (³T_1g ground state) and arises because of the large spin–orbit coupling, which gives diamagnetic ground state. The molecular orbital diagram of [ReCl₃(N–O)(PPh₃)] has been calculated with the density functional theory (DFT) method, and time-dependent DFT (TD-DFT) calculations have been employed in order to discussion of its spectroscopic properties in more detail.     

The Synthesis,Crystal, Molecular and Electronic Structure of [ReCl2(NO)(py)3]

In line with our investigations of rhenium nitrosyl complexes, we have studied the reaction of [ReCl₃(NO)(OPPh₃)(PPh₃)] with pyridine. The [ReCl₂(NO)(py)₃] complex obtained in this reaction has been characterised by IR, electronic spectra and magnetochemical measurements; ligand field parameters and the electronic structure have been determined. The crystal and molecular structure of [ReCl₂(NO)(py)₃] has been solved by the heavy atom method. Crystals of [ReCl₂(NO)(py)₃] contain distorted octahedral molecules with the pyridine ligands in the mer-arrangement. The nitrosyl group is coordinated linearly to the rhenium atom as NO⁺.     

The syntheses,crystal, molecular and electronic structures of two polymorphs of [ReCl2(N2COPh)(C3N2H4)(PPh3)2] and [ReCl2(N2COPh)(py)(PPh3)2] complexes

The [ReCl₂(η²-N₂COPh–N^′,O)(PPh₃)₂] complex reacts with pyridine and pyrazole to give [ReCl₂(N₂COPh)(py)(PPh₃)₂] and [ReCl₂(N₂COPh)(C₃N₂H₄)(PPh₃)₂], respectively. Two monoclinic polymers of [ReCl₂(N₂COPh)(C₃N₂H₄)(PPh₃)₂] and [ReCl₂(N₂COPh)(py)(PPh₃)₂] have been characterized by IR, UV–Vis, ¹H NMR, magnetic measurements and X-ray structure.     

Novel rhenium(III) complexes with 5,6-diphenyl-3-(2-pyridyl)-1,2,4-trazine: X-ray structures and DFT calculations for [ReCl3(OPPh3)(dppt)] and [ReCl3(PPh3)(dppt)] complexes

The reaction of [ReOCl₃(PPh₃)₂] with 5,6-diphenyl-3-(2-pyridyl)-1,2,4-trazine (dppt) has been examined and [ReCl₃(OPPh₃)(dppt)] has been obtained. The triphenylphosphine oxide can be easily replaced by PPh₃ in the reaction of [ReCl₃(OPPh₃)(dppt)] with an excess of triphenylphosphine. The [ReCl₃(OPPh₃)(dppt)] and [ReCl₃(PPh₃)(dppt)] complexes have been structurally and spectroscopically characterized. Their molecular orbital diagrams have been calculated with the density functional theory (DFT) method, and their electronic spectra have been discussed on the basis of time-dependent DFT calculations. The compound [ReCl₃(OPPh₃)(dppt)] has been studied additionally by magnetic measurement. The magnetic behavior is characteristic of mononuclear complexes with d⁴ low-spin octahedral Re(III) complexes (³T_1g ground state) and arise because of the large spin–orbit coupling (ζ = 2500 cm⁻¹), which gives diamagnetic ground state.     

Synthesis,spectroscopic investigation,structural characterization and DFT calculation of the complexes [ReX2(N2COPh)(4-PhPyr)(PPh3)2] (X = Cl, Br)

The reactions of [ReX₂(η²-N₂COPh-N′,O)(PPh₃)₂] with 4-phenylpyrimidine have been performed. As a result, the two complexes [ReX₂(N₂COPh)(4-PhPyr)(PPh₃)₂] (X = Cl, Br) (4-PhPyr = 4-phenylpyrimidine), isostructural in the solid state, have been obtained. The crystal and molecular structures of ([ReCl₂(N₂COPh)(4-PhPyr)(PPh₃)₂])₂·CHCl₃ (1) and ([ReBr₂(N₂COPh)(4-PhPyr)(PPh₃)₂])₂·CHCl₃ (2) have been determined. The electronic structure of [ReCl₂(N₂COPh)(4-PhPyr)(PPh₃)₂] has been examined using the density functional theory (DFT) method. The spin-allowed electronic transitions of 1 have been calculated with the time-dependent DFT method, and the UV–Vis spectrum of [ReCl₂(N₂COPh)(4-PhPyr)(PPh₃)₂] has been discussed on this basis.     

Struktur und ausgewählte Reaktionen von ReCl4(PPh3)2

ReCl₄(PPh₃)₂ – Reactions and Structure The compounds ReCl₄(PPh₃)₂ and Re₂OCl₃(C₂H₅COO)₂(PPh₃)₂ resulting from the reaction of ReOCl₃(PPh₃)₂ with PPh₃ in boiling propionic acid and HCl atmosphere were characterized by their VIS-spectra and structural data. Ligand exchange reactions with acetylacetone gave ReCl₂(acac)₂ as well as ReCl₂(acac)(PPh₃)₂. Crystallographic data see “Inhaltsübersicht”.     

Synthesis,spectroscopic investigation,structural characterization,and DFT calculations of [ReX2(N2COPh)(CH3PhCN)(PPh3)2] (X=Cl,Br)

Reactions of [ReX₂(η ²-N₂COPh-N′,O)(PPh₃)₂] with 3-methylbenzonitrile give two iso-structural complexes, [ReX₂(N₂COPh)(CH₃PhCN)(PPh₃)₂] (X?=?Cl, Br). The crystal and molecular structures of [ReCl₂(N₂COPh)(CH₃PhCN)(PPh₃)₂] (1) and [ReBr₂(N₂COPh)(CH₃PhCN)(PPh₃)₂]?·?CH₂Cl₂ (2) were determined. The electronic structures were examined with density functional theory (DFT). The spin-allowed electronic transitions were calculated with the time-dependent DFT method, and the UV-Vis spectrum has been discussed.     

Synthesis,spectroscopic investigation,crystal and molecular structure of [ReCl2(N2COPh)(C10H14N2)(PPh3)2]

[ReCl₂(N₂COPh)(C₁₀H₁₄N₂)(PPh₃)₂] has been obtained in the reaction of benzoylhydrazido-Re(V) with an excess of nicotine. The [ReCl₂(N₂COPh)(C₁₀H₁₄N₂)(PPh₃)₂] complex crystallizes in the monoclinic space group P2₁/n. The complex was characterized by infrared, Ultaviolet-visible, ¹H NMR and magnetic measurements.     

Rheniumkomplexe mit heterocyclischen Thiolen – Synthesen und Strukturen

Rhenium Compounds Containing Heterocyclic Thiols – Syntheses and Structures Reactions of trans‐[ReOCl₃(PPh₃)₂] with 1,3‐thiazoline‐2‐thiol (thiazSH), pyridine‐2‐thiol (pyrSH) or pyrimidine‐2‐thiol (pyrmSH) result in the formation of rhenium(V) oxo complexes or rhenium(III) species depending on the conditions applied. mer‐[ReOCl₃(thiazSH)(OPPh₃)], trans‐[ReCl₃(PPh₃)(thiazSH)₂], [ReO(2‐propO)(PPh₃)Cl(pyrS‐S,N)], cis‐[ReCl₂(PPh₃)₂(pyrS‐S,N)] and [ReCl₂(PPh₃)₂(pyrmS‐S,N)] have been isolated from such reactions and structurally characterized. cis‐[ReCl₂(PPh₃)₂(pyrS‐S,N)] and [ReCl₂(PPh₃)₂(pyrmS‐S,N)] are obtained in better yields by ligand substitution on trans‐[ReCl₃(MeCN)(PPh₃)₂]. The reaction between (n‐Bu₄N)[ReOCl₄] and purine‐6‐thiol (purinSH) gives the oxo‐bridged [O{ReO(purinS‐S,N)₂}₂].     

(PPh4)2[(SN)ReCl3(μ‐N)(μ‐NSN)ReCl3(THF)] – ein Nitrido‐Thionitrosyl‐Dinitridosulfato‐Komplex des Rheniums

(PPh₄)₂[(SN)ReCl₃(μ‐N)(μ‐NSN)ReCl₃(THF)] – a Nitrido‐Thionitrosyl‐Dinitridosulfato‐Complex of Rhenium The title compound has been prepared from PPh₄[Re^VIICl₄(NSCl)₂] with excess N(SiMe₃)₃ in dichloromethane solution to give red‐brown single crystals after recrystallisation from acetonitrile/THF solutions. As a by‐product PPh₄[ReNCl₄] is formed. (PPh₄)₂[(SN)ReCl₃(μ‐N)(μ‐NSN)ReCl₃(THF)] ( 1 ): Space group P2₁/n, Z = 4, lattice dimensions at –80 °C: a = 1024.1(1), b = 2350.2(1), c = 2315.4(2) pm, β = 94.09(1)°, R₁ = 0.0403. In the complex anion of 1 the rhenium atoms are connected by an asymmetric Re≡N–Re bridge as well as by a (NSN)^4–‐bridge to form a planar Re₂N(NSN) six‐membered heterocycle. Both rhenium atoms are coordinated by three chlorine atoms, one of them by a thionitrosyl ligand, the other one by the oxygen atom of a thf molecule.     

Novel dioxorhenium complex with bis(3,5-dimethypyrazol-1-yl)methane ligand – Synthesis,spectroscopic characterization,X-ray structure and DFT calculations

The reactions of [ReOBr₃(PPh₃)₂] and [ReOBr₃(AsPh₃)₂] with bis(3,5-dimethypyrazol-1-yl)methane (bdmpzm) have been examined and novel dioxorhenium(V) complex [ReO₂(bdmpzm)₂]Br · HBr · 2H₂O has been obtained. The compound has been studied by IR, UV–Vis, ¹H NMR spectroscopy, magnetization measurements and X-ray crystallography. The electronic structure of the [ReO₂(bdmpzm)₂]⁺ cation has been calculated with the density functional theory (DFT) method. The spin-allowed electronic transitions of [ReO₂(bdmpzm)₂]⁺ have been calculated with the TDDFT/PCM method, and the UV–Vis spectrum of [ReO₂(bdmpzm)₂]Br has been discussed on this basis.     

Synthesis,molecular and electronic structure of [ReCl2(N2COPh)(C4N2H4)(PPh3)2]

A new organodiazenido rhenium complex, [ReCl₂(N₂COPh)(C₄N₂H₄)(PPh₃)₂] has been obtained from the direct reaction of [ReCl₂(η²–N₂COPh–N′,O)(PPh₃)₂] with pyrazine in acetone. The complex has been characterized by spectroscopic methods and its structure determined using single-crystal X-ray diffraction techniques.     

Disproportionation of rhenium(V). Imidazolate coordination of pyridylbenzimidazole in a rhenium(III) complex

Reaction of trans-[ReOCl₃(PPh₃)₂] with 2-(2′-pyridyl)benzimidazole (pbiH) in methanol led to the isolation of the rhenium(III) compound [ReCl₂(pbi)(PPh₃)₂] (1). Complex 1 could also be prepared in better yield by the reduction of [ReO₄]^? with PPh₃ in the presence of pbiH and hydrochloric acid. An X-ray crystallographic study showed that pbi is coordinated as a bidentate monoanionic chelate, with deprotonation of the imidazolyl NH group. The PPh₃ ligands are trans to each other.     

Coordination chemistry of di-2-pyridylketone. Synthesis, spectroscopic investigations, X-ray studies and DFT calculations of Re(III) and Re(V) complexes

The paper presents a combined experimental and computational study of Re(III) and Re(V) complexes containing di-2-pyridylketone and its gem-diol form – [ReCl₃(dpk-N,O)(PPh₃)] (1), [ReCl₃(dpk-N,N′)(OPPh₃)] (2) and [ReOBr₃(dpk-OH)]·2(dpkH⁺Br⁻) (3). All the complexes have been characterized spectroscopically and structurally (by single-crystal X-ray diffraction). The complex 2 has been additionally studied by magnetic measurement. The magnetic behavior of 2 is characteristic of mononuclear octahedral Re(III) complex with d⁴ low-spin (³T_1g ground state) and arise because of the large spin–orbit coupling (ζ = 2500 cm⁻¹), which gives diamagnetic ground state. DFT and time-dependent (TD)DFT calculations have been carried out for [ReCl₃(dpk-N,N′)(OPPh₃)] and [ReOBr₃(dpk-OH), and their UV–vis spectra have been discussed on this basis.     

Two novel rhenium complexes derived from [ReO(OMe)Cl2(dpphen)] - Synthesis, crystal structure, spectroscopic and magnetic properties

The reaction of [ReO(OMe)Cl₂(dpphen)] (dpphen = 4,7-diphenyl-1,10-phenanthroline) with triphenylphosphine has been examined and two novel rhenium complexes - [Re^IIICl₃(dpphen)(PPh₃)]·Me₂CO (1) and [Re^IVCl₄(dpphen)]·CHCl₃ (2) - have been obtained. The compounds have been characterised by elemental analysis, IR, UV-Vis spectroscopy, magnetic measurements and X-ray crystallography. The electronic structures of [ReCl₃(dpphen)(PPh₃)] and [ReCl₄(dpphen)] have been studied by DFT/B3LYP level calculations, and TD-DFT calculations have been employed for discussion of the electronic spectra in more detail. The magnetic behaviour of 1 is characteristic of mononuclear complexes with d⁴ low-spin octahedral Re(III) complexes (³T_1g ground state) and arise because of the large spin-orbit coupling (ζ = 2500 cm⁻¹), which gives diamagnetic ground state. For complex 2 the results of calculations revealed value of zero-field splitting parameter D = 10.8 cm⁻¹, g_|| = 2.49 and g_⊥ = 1.51.     

Syntheses and properties of Re(III) complexes derived from hydrotris(1-pyrazolyl)methanes: molecular structure of [ReCl2(HCpz3)(PPh3)][BF4]

The complexes [ReCl₂{N₂C(O)Ph}(Hpz)(PPh₃)₂] (1) (Hpz = pyrazole), [ReCl₂{N₂C(O)Ph}(Hpz)₂(PPh₃)] (2), [ReCl₂(HCpz₃)(PPh₃)][BF₄] (3) and [ReCl₂(3,5-Me₂Hpz)₃(PPh₃)]Cl (4) were obtained by treatment of the chelate [ReCl₂{η²-N,O-N₂C(O)Ph}(PPh₃)₂] (0) with hydrotris(1-pyrazolyl)methane HCpz₃ (1,3), pyrazole Hpz (1,2), hydrotris(3,5-dimethyl-1-pyrazolyl)methane HC(3,5-Me₂pz)₃ (4) or dimethylpyrazole 3,5-Me₂Hpz (4). Rupture of a C(sp³)-N bond in HCpz₃ or HC(3,5-Me₂pz)₃, promoted by the Re centre, has occurred in the formation of 1 or 4, respectively. All compounds have been characterized by elemental analyses, IR and NMR spectroscopy, FAB-MS spectrometry, cyclic voltammetry and, for 1 · CH₂Cl₂ and 3, also by single crystal X-ray analysis. The electrochemical E_L Lever parameter has been estimated, for the first time, for the HCpz₃ and the benzoyldiazenide NNC(O)Ph ligands.     

Übergangsmetall—methylen-komplexe : XXXIV. Aufbau alicyclischer methylen-brucken nach einem modifizierten diazoalkan-verfahren

The mixed dinitrogen-isocyanide complexes mer-[ReCl(N₂)(CNMe)-{P(OMe)₃}₃] (I) and [ReCl(N₂)(CNMe)(PPh₃) {P(OEt)₃}₂] (II) are obtained by a novel route through reactions of CNMe with the organodiazenido species [ReCl₂(NNCOPh) {P(OMe)₃ }₃] and [ReCl₂(NNCOPh)(PPh₃){P(OEt)₃ }₂] (III, newly synthesized), whereas mer-[ReCl(N₂)(PPh₃) {P(OMe)₃ }₃] (IV) (which gives I by reaction with CNMe) is formed in the reaction of [$\text{ReCl}{}_2\text{(NNC}$OPh)(PPh₃)₂] with P(OMe)₃; the structure of complex I is authenticated by X-ray analysis.     

Cu(II), Cd(II) and Ni(II) azide complexes incorporating bis(3,5-dimethylpyrazol-1-yl)methane - Synthesis, spectroscopic characterisation, X-ray studies and magnetic properties

Three novel compounds [Cu₂(μ_1,1-N₃)₂(N₃)₂(bdmpzm)₂] (1) [Cd(N₃)₂(bdmpzm)]_n (2) and [Ni(N₃)₂(bdmpzm)₂] (3) have been synthesised and characterised structurally and spectroscopically. The structure 1 consists of a neutral dinuclear [Cu₂(μ_1,1-N₃)₂(N₃)₂(bdmpzm)₂] entities, compound 2 has one-dimensional zigzag chain structure extending along the crystallographic direction [1 0 0] with alternating di-μ_1,1-N₃ and di-μ_1,3-N₃ bridges, and 3 is a mononuclear complex. The experimental studies on the nickel(II) complex have been accompanied computationally by the density functional theory (DFT) calculations.