18399-62-7Relevant articles and documents
Insertion of phosphinidene complexes into the P-H bond of secondary phosphine oxides: A new version of the phospha-Wittig synthesis of P=C double bonds
Hao, Yanwei,Wu, Di,Tian, Rongqiang,Duan, Zheng,Mathey, Fran?ois
, p. 891 - 893 (2016/01/15)
Terminal phosphinidene complexes [RP-W(CO)5], as generated at 60 °C in the presence of copper chloride from the appropriate 7-phosphanorbornadiene complexes, react with secondary phosphine oxides Ar2P(O)H to give the insertion products into the P-H bonds. After metalation with NaH, these products react with aldehydes to give the corresponding phosphaalkenes which are trapped by dimethylbutadiene.
α-Phosphanyl amino acids: Synthesis, structure and properties of alkyl and heterocyclic N-substituted diphenylphosphanylglycines Dedicated to Professor Dr. Dr. h.c. Manfred Scheer on the occasion of his 60th birthday
Lach, Joanna,Peulecke, Normen,Kindermann, Markus K.,Palm, Gottfried J.,K?ckerling, Martin,Heinicke, Joachim W.
, p. 4933 - 4945 (2015/06/23)
N-Alkyl and N-heterocyclic substituted diphenylphosphanylglycines 1a-j were synthesized by a convenient one-pot, three-component reaction of diphenylphosphane, the corresponding primary amine and glyoxylic acid hydrate in diethyl ether. Phosphanylglycolates 2 and phosphoniobis(glycolates) 3 were detected as intermediates. In the case of steric hindrance or low basicity of the amine only 2 or mixtures of 2 and 1 are formed. Reactivity studies of selected phosphanylglycines showed facile decarboxylation and hydrolysis, oxidation and formation of coordination compounds with BH3 or W(CO)5. N-Alkyl derivatives (tert-butyl, n-hexyl, benzhydryl) with moderate steric hindrance reacted with Ni(COD)2 in THF or toluene in the presence of ethylene with heating under pressure to yield highly active oligomerization catalysts, and converting the ethylene to liquid and low-molecular-weight solid ethylene oligomers (MNMR 500-1250 g/mol) with high selectivity for linear α-olefins. Smaller N-alkyl or N-heterocyclic amino substituents at the phosphanyl acetic skeleton interfere with the ethylene conversion and deactivate the catalyst. The structures of the compounds were elucidated by solution NMR and single crystal XRD studies.
Syntheses, Reactivities and Molecular Structures of Tungsten Complexes containing the Diphenylphosphinodithioformato Ligand
Yih, Kuang-Hway,Lin, Ying-Chih,Cheng, Ming-Chu,Wang, Yu
, p. 1305 - 1314 (2007/10/02)
Treatment of 1 with CS2 afforded 3 which was also synthesized from the reaction of with 2.The reactions of 3 with various alkyl halides gave the neutral complexes , and the reactions of 3 with acyl halides gave > (R = Me or Ph).Both alkylation and acylation reactions occur at the sulfur atom.Treatment of 3 with afforded in which the two metal atoms were bridged by the PPh2CS2(1-) ligand.The reaction of 3 with (pip = piperidine) yielded and the dithiocarbamato tungsten complex .Complex 3 reacted with organic α,ω-diiodides (CH2I2, C2H4I2, C3H6I2), giving the phosphine bridged dinuclear complexes 2(μ-CH2)n> (n = 1-3), and only in the reaction of C3H6I2, was a mononuclear complex >> seen as a minor product.Complex 2(CO)2> was obtained from the reaction of 3 with oxalyl bromide in CH2Cl2.Thermolysis of 3 in tetrahydrofuran (thf) gave an anionic product identified as .All of the complexes were identified by spectroscopic methods.The structures of complexes 2, 3 and 4a were confirmed by single-crystal X-ray diffraction analyses.Crystal data: 2, monoclinic, space group P21, a = 10.244(4), b = 9.877(4), c = 11.124(3) Angstroem, β = 102.02(2) deg, Z = 2, R = 0.062, R' = 0.073 based on 1180 reflections with I > 2 ?(I); 3, triclinic, space group P, a = 10.688(3), b = 11.070(2), c = 12.785(2) Angstroem, α = 88.26(1), β = 81.87(2), γ = 74.081(17) deg, Z = 2, R = 0.028, R' = 0.025 based on 4557 reflections with I > 2?(I); 4a, triclinic, space group P, a = 9.177(5), b = 9.403(3), c = 12.461(6) Angstroem, α = 90.00(3), β = 103.85(4), γ = 94.79(3) deg, Z = 2, R = 0.041, R' = 0.041 based on 2442 reflections with I > 2?(I).
