85320-25-8Relevant academic research and scientific papers
AlCl3-catalyzed C-H p hosphination of benzene: A mechanistic study
Duan, Haodong,Gao, Jun,Guo, Ge,Han, Yuxi,Leng, Kangwei,Li, Xinjin,Wang, Zhongwei,Xu, Xiaolei,Yu, Qing
, (2021/01/06)
The characteristics of the reaction for the preparation of dichlorophenylphosphine (DCPP) via benzene and PCl3 in the presence of AlCl3 were studied. Some unique characteristics were observed when a catalytic amount of AlCl3 was used. Namely, more than one mole of DCPP was obtained per mole AlCl3, the reaction solution was layered, and DCPP could be directly separated. Our mechanistic study showed that benzene reacted with PCl3 to form DCPP-AlCl3, and DCPP-AlCl3 dissociated into DCPP and AlCl3, continuing to catalyze this reaction. This resulted in the high catalytic efficiency of AlCl3. The layering of the reaction solution was caused by the immiscibility of DCPP-AlCl3 with the raw materials, greatly facilitating the dissociation process of DCPP-AlCl3. The formation of diphenylphosphorus chloride (DPC) was due to a continuous Friedel-Crafts reaction between DCPP and benzene. DPC cooperated with AlCl3 to form the stable coordination compound DPC-AlCl3 that did not dissociate and was responsible for the deactivation of AlCl3.
Rhodium-Catalyzed Enantioposition-Selective Hydroarylation of Divinylphosphine Oxides with Aryl Boroxines
Wang, Zhe,Hayashi, Tamio
supporting information, p. 1702 - 1706 (2018/02/06)
The rhodium-catalyzed hydroarylation of divinylphosphine oxides (RP(O)(CH=CH2)2) with aryl boroxines ((ArBO)3) gives the corresponding monoarylation products (RP(O)(CH=CHAr)CH2CH3) in high yields. One of the two vinyl groups in the phosphine oxide undergoes oxidative arylation while the other one is reduced to an ethyl moiety. These reactions proceed with high selectivity in terms of the enantiotopic vinyl groups in the presence of (R)-DTBM-segphos/Rh to give the P-stereogenic monoarylation products with high enantioselectivity.
Chromium-Catalyzed Highly Selective Oligomerization of Ethene to 1-Hexene with N,N-Bis[chloro(aryl)phosphino]amine Ligands
H?hne, Martha,Peulecke, Normen,Konieczny, Katharina,Müller, Bernd H.,Rosenthal, Uwe
, p. 2467 - 2472 (2017/07/12)
Different N,N-bis[chloro(aryl)phosphino]amines were synthesized and characterized. The synthesized compounds were tested as ligands in the Cr-catalyzed oligomerization of ethene. The effect of the successive increase of the steric bulk either at one of th
Rhodium and Iridium Complexes of Bulky Tertiary Phosphine Ligands. Searching for Isolable Cationic MIII Alkylidenes
Campos, Jesús,Carmona, Ernesto
supporting information, p. 2212 - 2221 (2015/06/23)
Cyclometalated chloride complexes of rhodium and iridium based on (η5-C5Me5)MIII fragments that result from the metalation of the xylyl substituent of a coordinated PR2(Xyl) phosphine (Xyl = 2,6-Me2C6H3) have been prepared by reaction of the appropriate metal precursor with the corresponding phosphine. For iridium, the four complexes 1a-d, derived from the phosphines PiPr2(Xyl), PCy2(Xyl), PMe2(Xyl), and PPh2(Xyl), respectively, have been prepared, whereas for rhodium only the complexes 2a,d, derived from PiPr2(Xyl) and PMe2(Xyl), respectively, have been studied. Chloride abstraction from compounds 1 and 2 by NaBArF (BArF = B(3,5-C6H3(CF3)2)4) leads to either cationic dichloromethane adducts or to cationic hydride alkylidene structures resulting from α-H elimination. The rhodium complexes investigated yield only dichloromethane adducts. However, in the iridium system the less sterically demanding phosphines PMe2(Xyl) and PPh2(Xyl) also provide dichloromethane adducts as the only observable products, whereas for the bulkier PiPr2(Xyl) and PCy2(Xyl) ligands the hydride alkylidene formulation prevails. Nonetheless, variable-temperature NMR studies reveal that in solution each of these two structures exists in equilibrium with undetectable concentrations of the other by means of facile reversible α-H elimination and migratory insertion reactions. Reactivity studies on the cationic hydride alkylidene complexes of iridium are reported as well.
