A phase based approach to insulated molecular wires: Diplatinum octatetraynediyl complexes bearing fluorous trialkylphosphine ligands

作者：Clough Melissa C; Fiedler Tobias; Bhuvanesh Nattamai; Gladysz John A^*

来源：Journal of Organometallic Chemistry, 2016, 812: 34-42.

DOI：10.1016/j.jorganchem.2015.09.020

• Fluorous
• Phosphine ligand
• Polyyne
• Platinum
• Molecular wire
• Crystal structure

Reactions of [(tetrahydrothiophene)Pt(C6F5)mu-Cl](2) and fluorous phosphines P((CH2)(m)R-fn)(3) (R-fn = (CF2)(n-1)CF3; min = a, 2/8; b, 3/8; c, 3/10) afford the chloride complexes trans-(C6F5)((R-fn(CH2)(m))(3)P)(2)PtCl (8a-c, 40-74%), which upon treatment with butadiyne and CuI (cat.) in HNEt2/CF3C6H5 give trans-(C6F5) ((R-fn(CH2)(m))(3)P)(2)Pt(C C)(2)H (9a-c, 44-64%). Subsequent reactions with oxygen and CuCl/TMEDA in acetone yield the title complexes trans,trans-(C6F5)((R-fn(CH2)(m))(3)P)(2)Pt(C C)(4)Pt(P((CH2)(m)R-fn)(3))(2)(C6F5) (10a-c, 35-52%). All platinum complexes exhibit CF3C6F11/toluene partition coefficients of >99:<1. The crystal structure of 8b shows that the perfluoroalkyl groups segregate into fluorous domains. It was therefore thought that the perfluoroalkyl groups in 10a-c would aggregate about the polyynediyl chain. However, these adducts could not be crystallized. Electrochemical oxidations of 10a-c give radical cations that are much less stable than trialkyl and triarylphosphine analogs. Published by Elsevier B.V.

• 出版日期2016-6-15