117672-33-0Relevant academic research and scientific papers
Metal-free electrophilic phosphination of electron-rich arenes, arenols and aromatic thiols with diarylphosphine oxides
Yuan, Tao,Huang, Shenlin,Cai, Chun,Lu, Guo-Ping
supporting information, p. 30 - 33 (2017/12/27)
A new protocol for achieving the phosphination of arenes, arenols and thiols has been disclosed. This chemistry, in which diaryl(((trifluoromethyl)sulfonyl)oxy)phosphines as a kind of electrophilic phosphination reagents are in situ generated from diarylp
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.
General and selective copper-catalyzed reduction of tertiary and secondary phosphine oxides: Convenient synthesis of phosphines
Li, Yuehui,Das, Shoubhik,Zhou, Shaolin,Junge, Kathrin,Beller, Matthias
supporting information; experimental part, p. 9727 - 9732 (2012/07/14)
Novel catalytic reductions of tertiary and secondary phosphine oxides to phosphines have been developed. Using tetramethyldisiloxane (TMDS) as a mild reducing agent in the presence of copper complexes, PO bonds are selectively reduced in the presence of other reducible functional groups (FGs) such as ketones, esters, and olefins. Based on this transformation, an efficient one pot reduction/phosphination domino sequence allows for the synthesis of a variety of functionalized aromatic and aliphatic phosphines in good yields.
