Phosphororganische Verbindungen, 51. Die Einführung von Arylresten in tertiäre Phosphine mit Hilfe von Komplexen der übergangsmetalle (Komplexsalzmethode)

Abstract

Unter Mitwirkung der Chloride und Bromide von NiII, CoII, ZnII, CuII, MnII und FeII werden tertiäre Phosphine mit Arylchloriden, ‐bromiden und ‐jodiden in der Schmelze oder in siedendem Benzonitril in hohen Ausbeuten quartärisiert.

Room temperature quantum coherence in a potential molecular qubit

“…The deuterated derivatives 1CuD and 1NiD in which all hydrogen atoms of the PPh 4 þ counter ion have been replaced by deuterium were synthesized in the same manner. The salt PPh 4 Br-d20 was synthesized by literature methods 33 . In concentrated conditions, quantum coherence times are limited by intermolecular interactions between electron spins.…”

“…The compounds 1Cu and 1Ni were prepared according to a literature procedure, and were characterized by infrared, ultraviolet/ visible, elemental analysis, SQUID magnetometry and X-ray crystallography (Supplementary Information) 32 . Deuterated tetraphenylphosphoniumbromide was synthesized in a pressure cylinder with deuterated starting material according to a literature procedure 33 . The doped powder 1Cu 0.001% was prepared by rapid evaporation of an acetone solution of 1Cu and 1Ni in the correct molar ratio.…”

Nickel‐Catalyzed Synthesis of Phosphonium Salts from Aryl Halides and Triphenylphosphine

“…[18] However, the reaction was not highly chemoselective and many substituents on the aryl halide were not tolerated (vide infra). Horners nickel-mediated coupling [19] using nickel(II) salts as reagents also suffers from poor functional group tolerance, and it requires a high nickel loading (50 mol%) as well as high temperature (> 250 8C). [20] Although expensive nickel(0) complexes can be used as catalysts, a high loading (> 10 mol%) is required.…”

Tetraarylphosphonium Salts as Solubility‐Control Groups: Phosphonium‐Supported Triphenylphosphine and Azodicarboxylate Reagents

“…We felt that the elaboration of a phosphonium‐supported triphenylphosphine moiety would constitute an excellent model to evaluate the efficiency of the tetraarylphosphonium species as a potentially useful solubility‐control group. The desired compound 2 was synthesized using the Horner reaction,21 which involved a nickel‐mediated coupling of bromophosphine 1 and triphenylphosphine (Scheme ). A subsequent anion‐exchange reaction led either to the perchlorate or hexafluorophosphate salts 3 and 4 .…”