12148-71-9Relevant articles and documents
Formation and reactivity of an (alkene)peroxoiridium(iii) intermediate supported by an amidinato ligand
Kelley, Matthew R.,Rohde, Jan-Uwe
, p. 527 - 537 (2014)
An IrI complex of an acetamidinato ligand was synthesized by reaction of N,N′-diphenylacetamidine, PhNC(Me)NHPh, with either MeLi and [{Ir(cod)}2(μ-Cl)2] or [{Ir(cod)}2(μ-OMe) 2] and was characterized by X-ray crystallography as a mononuclear complex, [Ir{PhNC(Me)NPh}(cod)] (1; where cod = 1,5-cyclooctadiene). Reaction of 1 with CO afforded a dinuclear carbonyl complex, [{Ir(CO)2} 2{μ-PhNC(Me)NPh-κN:κN′}2] (2), as indicated by EI mass spectrometry and solution- and solid-state IR spectroscopy [νCO (n-pentane) = 2067, 2034 and 1992 cm-1]. Activation of O2 by 1 in solution at 20°C was irreversible and produced an (alkene)peroxoiridium(iii) intermediate, [Ir{PhNC(Me)NPh}(cod) (O2)] (3), which was characterized by one- and two-dimensional NMR techniques and IR spectroscopy (for 3, νOO = 860 cm-1; for 3-18O2, νOO = 807 cm-1). Complex 3 oxidized PPh3 to OPPh3, and its decay in the absence of added substrates followed by reaction with cod yielded 4-cycloocten-1-one and a minor amount of 1. In comparison with the results for the previously reported guanidinato complex [Ir{PhNC(NMe2)NPh}(cod) (O2)] (4), the formation of 3 and its reaction with PPh3 are significantly faster, indicating considerable ligand effects in these reactions.
Process for the synthesis of phenols from arenes
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Page 15-16, (2008/06/13)
A process to synthesize substituted phenols such as those of the general formula RR′R″Ar(OH) wherein R, R′, and R″ are each independently hydrogen or any group which does not interfere in the process for synthesizing the substituted phenol including, but not limited to, halo, alkyl, alkoxy, carboxylic ester, amine, amide; and Ar is any variety of aryl or hetroaryl by means of oxidation of substituted arylboronic esters is described. In particular, a metal-catalyzed C—H activation/borylation reaction is described, which when followed by direct oxidation in a single or separate reaction vessel affords phenols without the need for any intermediate manipulations. More particularly, a process wherein Ir-catalyzed borylation of arenes using pinacolborane (HBPin) followed by oxidation of the intermediate arylboronic ester by OXONE is described.