98546-51-1Relevant articles and documents
Gold-Carbon Contacts from Oxidative Addition of Aryl Iodides
Doud, Evan A.,Fu, Tianren,Roy, Xavier,Starr, Rachel L.,Stone, Ilana,Venkataraman, Latha
supporting information, p. 7128 - 7133 (2020/05/18)
Aryl halides are ubiquitous functional groups in organic chemistry, yet despite their obvious appeal as surface-binding linkers and as precursors for controlled graphene nanoribbon synthesis, they have seldom been used as such in molecular electronics. The confusion regarding the bonding of aryl iodides to Au electrodes is a case in point, with ambiguous reports of both dative Au-I and covalent Au-C contacts. Here we form single-molecule junctions with a series of oligophenylene molecular wires terminated asymmetrically with iodine and thiomethyl to show that the dative Au-I contact has a lower conductance than the covalent Au-C interaction, which we propose occurs via an in situ oxidative addition reaction at the Au surface. Furthermore, we confirm the formation of the Au-C bond by measuring an analogous series of molecules prepared ex situ with the complex AuI(PPh3) in place of the iodide. Density functional theory-based transport calculations support our experimental observations that Au-C linkages have higher conductance than Au-I linkages. Finally, we demonstrate selective promotion of the Au-C bond formation by controlling the bias applied across the junction. In addition to establishing the different binding modes of aryl iodides, our results chart a path to actively controlling oxidative addition on an Au surface using an applied bias.
Base free Suzuki acylation reactions of sodium (aryl trihydroxyborate) salts: A novel synthesis of substituted aryl ketones
Sithebe, Siphamandla,Molefe, Patience
, p. 305 - 311 (2017/07/13)
The first simple and efficient base free Pd(PPh3)4 catalysed synthesis of substituted aryl ketones from acyl chlorides and easily accessible sodium aryl trihydroxyborate salts in aqueous toluene is reported. The reaction conditions appeared versatile and tolerable to a variety of functional groups including, CF3, OMe, SMe, Br, NO2, F, OH and NH2 furnishing 25 examples of substituted aryl ketones in isolated yields of up to 96% in 24 h. Beside the high purity, the ease and convenience of the isolation compared to boronic acids, sodium aryl trihydroxyborate salts could be used subsequently without the addition of excess amount of an activator and are more user-friendly in terms of the use of accurate reaction stoichiometry.
Scalable, Metal- and Additive-Free, Photoinduced Borylation of Haloarenes and Quaternary Arylammonium Salts
Mfuh, Adelphe M.,Doyle, John D.,Chhetri, Bhuwan,Arman, Hadi D.,Larionov, Oleg V.
supporting information, p. 2985 - 2988 (2016/03/19)
We report herein a simple, metal- and additive-free, photoinduced borylation of haloarenes, including electron-rich fluoroarenes, as well as arylammonium salts directly to boronic acids. This borylation method has a broad scope and functional group tolerance. We show that it can be further extended to boronic esters and carried out on gram scale as well as under flow conditions.
