Synthesis and Structure of Sterically Crowded Triarylphosphine Bearing 4-Bromo-2,6-Bis(4-tert-Butylphenyl)Phenyl Group

Abstract

A novel sterically crowded triarylphosphine bearing a 2,6-diaryl-4-bromophenyl group, [4-bromo-2,6-bis(4-tert-butylphenyl)phenyl]bis(2,4,6-triisopropylphenyl)phosphine (1), was synthesized. The X-ray crystallography revealed that the bond angles and lengths around the phosphorus atom (110.9°, 1.846 Å) are comparable to those of tris(2,4,6-triisopropylphenyl)phosphine and its derivatives. Triarylphosphine 1 is reversibly oxidized to the radical cation at the potential close to that of the typical sterically crowded (bromoaryl)phosphine, (4-bromo-2,6-diisopropylphenyl)bis(2,4,6-triisopropylphenyl)phosphine, and exhibits the UV absorption at long wavelength (λ_max 332 nm) characteristic of the sterically crowded triarylphosphines. Thus, triarylphosphine 1 can be regarded to be a promising candidate for the key synthetic intermediate or building block to the functional molecules bearing sterically crowded triarylphosphine moieties.     

Synthesis,Crystal Structure,and Properties of a Dinuclear Cu(I) Cluster

Abstract

A new dinuclear copper(I) cluster complex, [(o-Tol)₃PCuI₂CuP(o-Tol)₃(DMF)] (1) ((o-Tol)₃P = tris(2- methylphenyl)phosphine, DMF = N, N′-dimethylformamide), has been synthesized and the crystal structure was determined by a single-crystal X-ray diffraction study. The dinuclear copper(I) cluster molecule containing an asymmetric Cu₂I₂P₂O core and the dinuclear clusters are fused together by a strong π–π stacking interaction to form asupramolecular one-dimensional (1D) chain. After having compared the relevant complexes composed of CuI and monodentate triarylphosphine ligands, the impact of the substituent of the triarylphosphine ligand to the subsequent complex structure has also been discussed.Except for a strong π–π* bond, the complex 1 also exhibits a weak metal-to-ligand charge transfer (MLCT) absorption bond in the 430–530-nm region and displays a weak green-yellow emission when irradiated by ultraviolet (UV) light. The thermogravimetric analysis demonstrates that its thermal stability is good, and the corresponding PXRD analysis has revealed that the final, organic-free decomposed product is CuI.     

REACTIONS OF ARSINIC AND ARSONIC ACIDS WITH H2S AND H2Se: CRYSTAL STRUCTURE OF 1,4-DIPHENYL-1,4-DIARSA-2,3,5-TRISELENACYCLOPENTANE

Abstract

The reactions of a series of arsinic and arsonic acids with hydrogen sulfide and hydrogen selenide have been investigated. The various arsinic acids were found to produce a variety of products, but the reaction was characterized by the reduction of arsenic(V) to arsenic(III), loss of hydroxyl groups bonded to arsenic and, to a lesser degree, the rupture of arsenic-carbon bond(s). Phenylcarboxymethylarsinic acid yielded, on reaction with H₂S or H₂Se, 1,4-diphenyl-1,4-diarsa-2,3,5-trichalocogenapentanes, where the chalcogen atom is S or Se. Arsonic acids yielded as final products compounds having a range of stoichiometries ranging from RAsS to R-7As₂S₃. 1,4-Diphenyl-1,4-diarsa-2,3,5-triselenacyclopentane consists of a non-planar, five-membered ring in which the As–C bond distances are 1.962 Å, the As—Se bond distances are 2.388 Å and the Se—Se bond distance is 2.334 Å. The bond distances are very close to those which are expected for single, covalent bonds.     

Vibrational spectra and molecular conformations of unbranched dialkyl selenides

The IR and Raman spectra of six unbranched dialkyl selenides, namely ethylmethyl selenide, methylpropyl selenide, butylmethyl selenide, diethyl selenide, ethylpropyl selenide and dipropyl selenide, have been systematically investigated. The spectra are analysed on the basis of the spectral examination and the normal coordinate treatment. The CH₂-Se stretching wavenumbers of the dialkyl selenides correlate well with the conformation about the CSe-C-C bond axes. The molecular conformation in the solid and liquid states is studied by utilizing this correlation in conjunction with the wave-numbers of the CH₂ rocking and skeletal deformation vibrations. The conformational stability in the liquid state is also examined and the enthalpy difference between the trans and gauche forms of ethylmethyl selenide is obtained as 0.22 ± 0.05 kcal mol^?1, the gauche form being more stable. The conformational stability of dialkyl ethers, sulphides and selenides are comparatively discussed.     

Organoselenide as a Novel Ionophore for a Silver-Selective Membrane Electrode

Abstract

Three selenium-containing compounds, diphenyl selenide, benzyl phenyl selenide and dibenzyl selenide were used as neutral carriers to make a Ag⁺-selective membrane electrode. All three compounds exhibited higher sensitivity to Ag⁺ than the corresponding sulfides and ethers. The highest sensitivity was obtained by dibenzyl selenide and an electrode constructed using this carrier and bis(l-butylpentyl) adipate as a membrane solvent in a poly(vinyl chloride) membrane matrix exhibited a near-Nernstian response to Ag⁺ in the concentration range from 1 x 10^?5 to 1 x 10^?2 M with a slope of 52 mV per concentration decade. The lower limit of detection was around 1 μM. The ion selectivity of this electrode for Ag⁺ was over 10⁴ times that for other metal cations. Dibenzyl selenide and Ag⁺ interactions were examined by ¹H-NMR spectroscopy.     

Reaction of Halidemethyldithio- and Selenothiophosphonic Acids with Alkylthiocyanates – A Novel Method of Synthesizing P,N, S (Se) – Containing Heterocycles

Abstract

Novel heterocyclic derivatives - 1,3,4-thiazaphospholines and 1,3,4-selenoazaphospolines 7, were obtained passing hydrogen sulfide or hydrogen selenide 2 through the solution of 0-phenylchloromethyl (chloro)thiophosphonate 1 and alkylthiocyanate followed by addition of triethylamine. It is assumed that 0-phenylchloromethylthiophosphonic and -selenophosphonic acids 3 are formed at the first stage, which further add to CN triple bond of alkylthiocyanates 4 to produce S- or Se-thiophosphonyldithio- or selenothioiminocarbonates 5. The latter undergo phosphorotropic rearrangement into appropriate S-thiophosphonyl dithio- or selenothiocarbamates 6.     

Reactions of methyltris(triarylphosphine)cobalt : I. Formation of biaryls

Methyltris(triarylphosphine)cobalt (Ar₃P)₃CoCH₃, decomposes in solutions of THF, benzene or chlorobenzene to yield biaryls. Coupling to biaryls occurs at the ring carbon originally bonded to phosphorus. Mixed biaryls are obtained from crossover reactions of complexes bearing different triarylphosphine ligands and reactions of complexes with free triarylphosphines.     

Design and synthesis of tris[bis(benzylammonium)aryl]phosphines with bulky meta-substituents

A novel 3,5,3′,5′,3″,5″-hexakis(dimethylamino)methyl substituted triphenylphosphine analogue has been prepared. The six amine functionalities of the corresponding phosphine oxide and sulfide were alkylated quantitatively with methyl iodide and benzyl bromide, as well as with G1 and G2 Fréchet dendrons to afford the respective hexa-ammonium triarylphosphine oxides and sulfides. The phosphine sulfide derivatives were deprotected with P(n-Bu)₃ to afford a series of hexa-ammonium triarylphosphines that range from small molecules to first and second generation dendrimers (MW up to 5451.44). Upon formation of the hexa-ammonium salt a clear shift in ³¹P NMR is observed, indicative for opening of the C-P-C angle of the triaryl phosphine. Calculations on the hexacationic phosphines show an increased barrier of rotation around the P-C(aryl) bond with increasing size of the N-substituents. The calculated structure of the G2-dendron alkylated hexa-ammonium triarylphosphine shows that this dendritic phosphine has a disc-like rather than a cone-like structure, with an estimated cone angle of approximately 180°     

Scalable Rhodium(III)‐Catalyzed Aryl C−H Phosphorylation Enabled by Anodic Oxidation Induced Reductive Elimination

Transition metal catalyzed C?H phosphorylation remains an unsolved challenge. Reported methods are generally limited in scope and require stoichiometric silver salts as oxidants. Reported here is an electrochemically driven Rh^III‐catalyzed aryl C?H phosphorylation reaction that proceeds through H₂ evolution, obviating the need for stoichiometric metal oxidants. The method is compatible with a variety of aryl C?H and P?H coupling partners and particularly useful for synthesizing triarylphosphine oxides from diarylphosphine oxides, which are often difficult coupling partners for transition metal catalyzed C?H phosphorylation reactions. Experimental results suggest that the mechanism responsible for the C?P bond formation involves an oxidation‐induced reductive elimination process.     

Pyrolysis of Dibenzyl Selenides to Bibenzyls

The formation of carbon-carbon bond by sulfur extrusion such as pyrolysis of cyclic sulfones is well known as an important synthetic method, especially for the synthesis of cyclophane framework.¹⁾ Little is known about selenium extrusion as the counterpart, though organoseleniums have been properly appreciated as a useful tool for manipulating a functional group.²⁾ Lardon reported that the thermal decomposition of dibenzyl diselenide led to a mixture of dibenzyl selenide and polyselenides.³⁾ In contrast, recent reports showed that at 210°C, heating bis(diphenylmethyl) diselenide resulted in ready selenium extrusion to 1,1,2,2-tetraphenylethane⁴⁾, and dianthrylmethyl mono- and diselenides to 1,2-dianthrylethane.⁵⁾ Therefore,- it is worthwhile to study the thermal behavior of dibenzyl selenide itself.     

THE REARRANGEMENT OF ARYLSELENENAMIDES

Abstract

Attempts to synthesize N-phenylbenzeneselenena mide always produced the isomeric p-aminodiphenyl selenide, probably as a result of an acid catalyzed rearrangement. The ease with which this rearrangement occurs is contrasted with the forcing conditions required for the analogous rearrangement of sulfenamides.     

A NEW APPROACH TO ISOLEVOGLUCOSENONE VIA THE 2,3-SIGMATROPIC REARRANGEMENT OF AN ALLYLIC SELENIDE

A convenient method is described for the synthesis of isolevoglucosenone 5, via allylic selenide 3, and its rearrangement to allylic alcohol 4, followed by oxidation with manganese oxide. Isolevoglucosenone 5, is produced in 62% overall yield.     

Metal-Selenium Interactions. Crystal Structures of [Dihalo-{1, 1'-Methylene-Bis(Diphenyl Phosphine Selenide)}] Mercury(II) Complexes

Crystal structures of mercury(II) complexes with a bis(tertiary phosphine selenide), namely 1,1'-methylenebis(diphenylphosphine selenide) $\{{\rm Ph_2P(Se){{\hskip -1pt -\!\!\!- \hskip-.5pt}} CH_2{{\hskip -1pt -\!\!\!- \hskip-.5pt}} P(Se)Ph_2,\ dpmSe_2}\}$     

Enhancement of Sensitivity for Selenium Determination in Atomic Absorption Spectrophotometry by Introducting Hydrogen Selenide into an Argon-Hydrogen Flame

Abstract

The sensitivity for selenium determination with atomic absorption spectrophotometry is enhanced to a large extent by introducing hydrogen selenide gas into an argon-hydrogen flame. As a reducing agent, zinc granular and stannous chloride is successfully used for quantitative and rapid productions of hydrogen selenide from selenium(IV) solution. The sensitivity for 1 % absorption of the signal is estimated to be about 0.02 ppm of selenium.     

Gold(I) Complexation with Trialkyl/Triaryl Phosphine Selenide Ligands

Abstract

A number of phosphine selenide ligands and their gold(I) complexes of general formula R₃P?Se?Au?X (where X is Cl^?, Br^? and CN^? and R = phenyl, cyclohexyl and tolyl) were prepared. The complexes were characterized by elemental analysis, IR and ³¹P NMR spectroscopic methods. In the IR spectra of all complexes a decrease in frequency of P?Se bond upon coordination was observed, indicating a decrease in P?Se bond order. ³¹P NMR showed that the electronegativity of the substituents is the most important factor determining the ³¹P NMR chemical shift. It was observed that phosphorus resonance is more downfield in alkyl substituted phosphine selenides, as compared to the aryl substituted ones. Ligand disproportionation in the complex Cy₃P?SeAuCN in solution to form [Au(CN)₂]^? and [(Cy₃P?Se)₂Au]⁺ was investigated by ¹³C and ¹⁵N NMR spectroscopy.     

Multinuclear NMR Studies of the Substitlent Effects in N-Phenyl-P,P,P-Triarylphospha-λ5-Azenes,Triaryl-Phosphines and Triarylphosphine Oxides

Abstract

A series of N-phenyl-P,P,P-triarylphospha-λ⁵-azenes (1) as well as their ^l5N labeled analogs was synthesized. The ¹³C, ³¹P, and ¹⁵N NMR spectra of this series and those of two other series of related compounds, namely triarylphosphines (2) and triarylphosphine oxides (3), were measured and are reported. Many satisfactory correlations using the mono-substituent parameter (MSP) and the Taft dual-substituent parameter (DSP) treatments with the ¹³C substituent chemical shifts (SCS), ³¹P SCS, ¹⁵N SCS and the one bond P-N, P-C and C-N coupling constants were observed and will be discussed. Thus, for example, the ³¹P and ¹⁵N chemical shifts in 1 correlated with [sgrave]^?with negative slopes while the ³¹P chemical shifts in 3 correlated with those in 1 with a slope of 2.0. The ¹³C chemical shifts in 1 correlated excellently with the corresponding ones in 3 with slopes very close to unity. The substituent effects on the chemical shifts of the various nuclei were shown to be mainly due to changes in the charge distribution on those nuclei. In 1 the one bond P-N and P-C coupling constants correlated with [sgrave]_p and [sgrave]_R respectively. The one bond P-C coupling constants of 1 correlated quite well with those of 3 with a slope of 0.93 while the corresponding correlation of 1 with 2 was quite poor. Taft DSP treatment of ¹J_PCin 1 and 3 were quite similar, ρI and ρR were both negative and ρR was much larger than ρI. Series 2 showed behavior which was different from that shown by 1 and 3 but similar to that shown by other systems with a lone electron pair on the atom bound to the phenyl ring. The substituent effects on the one bond P-N, P-C and C-N coupling constants will be discussed in terms of bonding and hybridization changes between the directly bonded nuclei.     

Anomeric effect and theoretical vibrational spectra compared to the experiment in 2-chloro-1,3,2-dioxaphosphorinane-2-oxide, -sulfide,and -selenide. I. Anomeric effect and structures

2-Chloro-1,3,2-dioxaphosphorinane-2-oxide, -sulfide, and -selenide are studied at the DFT/B3LYP level and several ab initio methods using a 6-311G** basis set. Our energy optimizations by all these methods show that for oxide DFT and ab initio methods are not much different, while for the sulfide and the selenide the DFT relative energies are higher by about a kcal/mol as compared to those of MP2, MP3, MP4(SDTQ)//MP2, and CCSD(T)//MP2 (//MP2 indicates that a single-point calculation based on the MP2 optimized geometry is performed). However, regardless of rather large relative energies, that does not change the fact that in all three cases the conformational equilibrium mixture contains more than 95% of the lowest, chair-equatorial conformer (this indicates that the P=X bond is in equatorial position). This one and the next higher conformer (chair-axial) are confirmed to be real conformers (energy minima) in all cases. The energetically much higher twist and boat forms are probably just stationary states and local maxima because in many cases, geometry optimizations do not converge to them. Only for MP2 and the selenide do all optimizations converge to the desired stationary state. The relative energies could all be explained in terms of anomeric effects and ring strains. The decreasing covalent character of the P=X bond, with X changing from O to S and to Se, shows itself in the increasing bond lengths and the decreasing strength of anomeric effects.     

2-Arylethenyl-2″-Arylethynyl Sulfones: A Potential Source for New Heterocycles

Abstract

Different heteroatoms viz., N, S & Se have been incorporated into 2-arylethenyl-2′-arylethynyl sulfones by nucleophilic reaction with benzylmine, hydrogen sulfide and sodium hydrogen selenide.     

Making Aromatic Phosphorus Heterocycles More Basic and Nucleophilic: Synthesis,Characterization and Reactivity of the First Phosphinine Selenide

The synthesis and isolation of a phosphinine selenide was achieved for the first time by reacting red selenium with 2,6-bis(trimethylsilyl)phosphinine. The rather large coupling constant of ¹J_P,Se=883 Hz is in line with a P−Se bond of high s-character. The σ-electron donating Me₃Si-substituents significantly increase the energy of the phosphorus lone pair and hence its basicity, making the heterocycle considerably more basic and nucleophilic than the unsubstituted phosphinine C₅H₅P, as confirmed by the calculated gas phase basicities. NBO calculations further reveal that the lone pairs of the selenium atom are stabilized through donor-acceptor interactions with antibonding orbitals of the aromatic ring. The novel phosphinine selenide shows a distinct reactivity towards hexafluoro-2-butyne, Au(I)Cl as well as ⁱPrOH. Our results pave the way for new perspectives in the chemistry of phosphorus in low coordination.