Mercuration of a ruthenocene. Synthesis, characterization, and halogenation of [[C5(HgOAc)5](C5Me5)Ru]

Double Friedel–Crafts Acylation Reactions on the Same Ring of a Metallocene: Synthesis of a 2,5‐Diacetylphospharuthenocene

“…In mechanistic terms, the results have been interpreted as implying that the pathway of electrophilic aromatic substitutions in simple metallocenes varies as a function of the electrophile. Experimentally, mercurials and other soft electrophiles that give polysubstitution [103][104][105][106][107] are assumed to follow a metal-assisted endo-attack trajectory; [108] harder electrophiles such as acyl groups have been proposed, on the basis of isotope scrambling studies, to make an exo attack. [109] It has also been suggested from experimental studies that any subsequent acylation of the second ring may switch to an endo pathway.…”

Tenfold Metalation of Ferrocene: Synthesis, Structures, and Metallophilic Interactions in FeC10(HgX)10

“…Mercuration of aromatic systems by Hg 2+ proceeds mechanistically via an electrophilic substitution pathway [27] . Surprisingly, the reaction seems to proceed even faster with increasing degree of mercuration [28] . Unfortunately, the insolubility of Winter's highly mercurated metallocenes prevented their full spectroscopic characterization.…”

“…[27] Surprisingly,t he reaction seemst oproceed even fasterw ith increasing degree of mercuration. [28] Unfortunately,the insolubility of Winter's highly mercuratedm etallocenes prevented their full spectroscopic characterization.M oreover,t he permercuration of ferrocenes eemed also to be incomplete. [29] In ar eview article, it was mentioned that the solubility and the degree of mercuration could be improvedbyreplacing mercury(II)acetate by mercury(II) butyrate, but detailsw ere never published.…”

Ruthenocenes and Osmocenes

“…19 Examples o f ruthenocenes with staggered rings (because of inter-ring steric repulsion between substituents) include RuCp*[r|-C 5 X(CF 3 ) 4 ] (X = H and OSiEt 3 ) 20 and RuCp*(r|-C 5 I 5 ). 39 Many other ruthenocene and osmocene derivatives have been structurally characterized and a full listing is given in Volume 13.…”