Organometallic electron reservoirs. 5. Novel mode of carbon-hydrogen activation using dioxygen via superoxide radical anion in solution and in the solid state with C5R5FeIC6R'6. Subsequent bond formation with carbon, silicon, phosphorus, manganese, iron, chromium, and molybdenum

The Remarkable Effect of the Manganese Ion with Dioxygen on the Stability of π‐Conjugated Radical Cations

“…Also, these results give the first direct observation of the role of oxygen in the special salt effect, which was previously proposed by Astruc’s group (Scheme ) 2. 10–12…”

Quaternized and Thiazole‐Functionalized Free Radical‐Generating Organometallic Dendrimers as Antimicrobial Platform against Multidrug‐Resistant Microorganisms

“…This finding is exciting as it demonstrates for the first time that 18‐electron iron sandwich complexes spontaneously generate transient radicals. Indeed, their counterparts, the 19‐electron, and 17‐electron iron sandwich complexes are well‐known to form radicals, which account for their well‐exploited biological activity . Here, the mechanistic scenario leading to the formation of these radicals and their exact nature are yet to be understood and is a goal of a future study.…”

Organoiron-mediated dendrimer syntheses with 1→3 connectivity and applications

“…26,27 The interest in such an increase of the acidity of the benzylic protons was first realized thirty years ago when the yellow toluene complex was deprotonated by t-BuOK in THF to a deep-red cyclohexadienylmethylene complex 1 (Scheme 4), especially because deprotonation could be followed by alkylation with MeI and various electrophiles to form C-C and C-element bonds. [28][29][30] Moreover, deprotonation could also be obtained upon reaction of O 2 or air with the corresponding neutral 19-electron Fe I complexes (for instance 2, R¼Me) that resulted from single electron reduction of [Fe II (h 6 -ArMe)(h 5 -C 5 H 5 )] þ [X] (Scheme 5). [31][32][33][34][35] Simple one-pot procedures were disclosed to polyfunctionalize the polymethylbenzenes using KOH and allyl bromide in tetrahydrofuranne (THF) or 1,2-dimethoxyethane (DME) under ambient conditions (Scheme 6).…”

“…With the hexamethylbenzene complex 3, however, perallylation can be stopped after the first allylation, because of the steric bulk, and the hexabutenyl star complex obtained can be easily isolated after 24 h. The second allylation is much slower than the first, but, after three weeks, the dodeca-allylated complex could be synthesized. 29 With durene, the octa-allylation is easy in two days. 43 [Fe(h 6 -mesitylene)(h 5 -C 5 H 5 )][PF 6 ], 4, nona-allylation is achieved in three days under ambient conditions, 44 and this latter reaction is the most useful for dendrimer syntheses, because it quantitatively provides a remarkable pre-dendritic iron complex 5 on a large scale.…”

“…56,57 Thus, iteration of the sequence consisting of hydrosilylation with chloro methyldimethylsilane 58,59 followed by nucleophilic substitution of chloride by iodide and of iodide by the phenolate dendron could be pursued until the Ninth generation that contains a theoretical number of 177,147 (i. e. 3 11 ) allyl branches (Scheme 10). After each reaction, completion was checked by 1 H, 13 C and 29 Si NMR until G9. The dendrimers are very soluble in CDCl 3 , even up to G9, and the NMR spectra clearly show the peripheral dendrimer groups (the inside groups being too few to observe, especially with a growth involving 1/3 connectivity).…”