2215-36-3Relevant academic research and scientific papers
CHEMIE POLYFUNKTIONELLER MOLECUELE XCI*. TRITERTIAERE ARSINE UND IHRE VERWENDUNG ALS BAUSTEINE ZUR SYNTHESE VON ARSENHALTIGEN CRYPTANDEN (BZW. SPHERANDEN)
Ellermann, Jochen,Veit, Adolf,Moll, Matthias
, p. 51 - 66 (1986)
Cl (V), 3>Cl (VII) and the 1,3,5-trithiacyclohexane derivative (CHS)3(CH2CH2Cl)3 (IX) react with NaAs(C6H5)2 in liquid ammonia to give N2CH2CH(CH3)As(C6H5)2 (VI), N3 (VIII) and (CHS)33 (X).Treatment of VI with HI results, under elimination of benzene, almost quantitatively in the formation of I (XI), which is recristallized from THF as I*THF (1/1) (XIa).All attempts to obtain homogeneous products by reaction of VIII or X with HI, such as 3>I and (CHS)3(CH2CH2AsI2)3, failed.With H2O/NH3 or H2S/N(C2H5)3 XIa forms the cryptands 8(As4O4)6 (XII) or 8(As4O4)6 (XIII), which also can be considered as spherands.All the new compounds are characterized, as far as possible, by their IR, Raman, 1H NMR and mass spectra.
THE REACTIONS OF DIPHENYLLITHIOARSINE AND DIPHENYLARSINE WITH ALDEHYDES
Busse, P. J.,Hrung, C-P.,Irgolic, K. J.,O'Brien, D. H.,Kolar, F. L.,Seoud, Omar A. El
, p. 1 - 8 (1980)
Diphenyllithioarsine reacts with aldehydes (RCHO, R=CH2CH3, CH(CH3)2, and Ph) to form lithium salts of α-hydroxyalkylarsines.Protonation of the lithium salts gives α-hydroxyalkylarsines.Diphenylarsine reacts with aldehydes below room temperature in the absence of solvents to produce white solids.The reactions are rapid in the presence of acid catalysts.Proton and carbon-13 NMR, infrared and Raman spectra show that the products are diphenyl-(α-hydroxyalkyl)arsines, Ph2AsCHOHR.These compounds are thermally unstable.In organic solvents, equilibrium is established between the α-hydroxyalkylarsines and the aldehyde and diphenylarsine.
Investigating palladium pincer complexes in catalytic asymmetric hydrophosphination and hydroarsination
Tay, Wee Shan,Yang, Xiang-Yuan,Li, Yongxin,Pullarkat, Sumod A.,Leung, Pak-Hing
, p. 4602 - 4610 (2019/04/05)
Given the periodic relationship of phosphines and arsines, is remodeling the catalytic asymmetric hydrophosphination reaction an efficient manner to develop the corresponding hydroarsination reaction? Herein, a chiral PCP-Pd(ii) pincer complex adept at ge
Mechanistic variety in zirconium-catalyzed bond-forming reaction of arsines
Roering, Andrew J.,Davidson, Jillian J.,MacMillan, Samantha N.,Tanski, Joseph M.,Waterman, Rory
supporting information; experimental part, p. 4488 - 4498 (2009/02/04)
Triamidoamine-supported zirconium complexes have been demonstrated to catalyze a range of bond-forming events utilizing arsines. Three different mechanisms have been observed in these reactions. In the first mechanism, triamidoamine-supported zirconium complexes of the general type (N 3N)ZrX (N3N = N(CH2CH2NSiMe 3)33-; X = monoanionic ligand) catalyzed the dehydrogenative dimerization of diphenylarsine. Mechanistic analysis revealed that As-As bond formation proceeds via σ-bond metathesis steps similar to the previously reported dehydrocoupling of phosphines by the same catalysts. In the second mechanism, sterically encumbered primary arsines appear to be dehydrocoupled via α elimination of an arsinidene fragment. Dehydrocoupling of dmpAsH2 (dmp = 2,6-dimesitylphenyl) to form (dmp)As = As(dmp) by (N3N)Zr-complexes appeared to proceed via elimination of dmpAs: from the arsenido intermediate, (N3N)ZrAsH(dmp) . Further support for α-arsinidene elimination came from the thermal decomposition of (N3N)ZrAsHMes (9) to (MesAs)4 (10), which obeyed first-order kinetics. In the third mechanism, the observation of stoichiometric insertion reactivity of the Zr-As bond with polar substrates, PhCH2NC, PhCN, (1-napthyl)NCS, and CS2, led to the development of intermolecular hydroarsination catalysis of terminal alkynes. Here, (N3N)ZrAsPh2 (2) catalyzed the addition of diphenylarsine to phenylacetylene and 1-hexyne to give the respective vinylarsine products. Arsenido complexes 2 and 9 and tetraarsine 10 have been structurally characterized.
Thioacylsulfanylarsines (RCS2)xAsPh3-x, x = 1-3: Synthesis, structures, natural bond order analyses and reactions with piperidine
Tani, Kazuyasu,Hanabusa, Shin-Ichi,Kato, Shinzi,Mutoh, Shin-Ya,Suzuki, Shun-Ichi,Ishida, Masaru
, p. 518 - 527 (2007/10/03)
A series of thioacylsulfanylarsines ((RCS2)AsPh2, (RCS2)2AsPh, (RCS2)3As) were synthesized by treating piperidinium dithiocarboxylates with Ph2AsCl, PhAsCl2 or AsCl3, respectively and characterized. Their molecular structures were determined by X-ray crystallography and compared with those of the corresponding acylsulfanyl derivatives ((RCOS)AsPh2, (RCOS)2AsPh, (RCOS)3As). They exist as monomers, and the environment around the arsenic atoms is distorted tetrahedral with one lone pair at the apex. The structure of the mono(dithiocarboxylate) is different from that of the corresponding thiocarboxylic acid derivative, while the bis and tris derivatives showed similar structure to the corresponding thiocarboxylic acid derivatives ((RCOS)2AsPh, (RCOS)3As), respectively. The new compounds showed intramolecular interactions between the thiocarbonyl sulfur and the central arsenic atom. NBO (Natural Bond Orbital) analyses performed on the model compounds (CH3CS2)As(CH3)2 and (CH3CS21)-(CH3CS22 )AsCH3 at the RHF/LANL2DZ level of theory showed the presence of interactions between the non-bonding orbitals on the thiocarbonyl sulfur (ns) and the σ*MS orbitals together with that between the ns and the σ*MC orbitals for the former compound; for the latter the presence of both orbital interactions between ns and σ*MS1 and between ns and σ*MS2 are present. The reaction of the mono(dithiocarboxylate) derivative (R = 4-CH3-C6H4) with piperidine in ethanol gave piperidinium diphenyldithioarsinate along with the corresponding N-thioacyl- or N-acyl-piperidine. A similar reaction of the bis(dithiocarboxylate) derivative (R = 4-CH3C6H4) gave the novel di(piperidinium) phenyltrithioarsonate in which two anion charges are delocalized on the AsS3 moiety and a cyclic phenylarsine sulfide tetramer (PhAsS)4. The diphenyldithioarsinate and phenyltrithioarsonate salts exist as a dimer and a polymer, respectively, in which 12-membered rings are formed by intermolecular N-H ... S hydrogen bonds.
ORGANOARSENEVERBINDUNGEN: 39 SUBSTITUERTE BENZYLPHOSPHINE UND -ARSINE ALS LEICHT ZUGAENGLICHE BIDENTATE LIGANDEN
Kellner, K.,Rothe, S.,Steyer, E.-M.,Tzschach, A.
, p. 269 - 274 (2007/10/02)
2-Hydroxybenzylamines or 2- and 4-aminobenzylamines react with diphenylphosphine at higher temperature to give hydroxy-substituted and aminosubstituted benzylphosphines, respectively.This reaction fails in the case of alkoxy or dialkylaminobenzyl amines.T
