A beneficial effect of ortho-substituents in the arylation of (benzene)tricarbonylmanganese(1+) hexafluorophosphate(1−)

Heteropolymetallic Complex Syntheses by Reiterative Nucleophilic Additions of Lithiated (η6-Arene)tricarbonylchromium Compounds to Cationic (η6-Benzene)manganese Complexes

“…It has been observed that single electron transfer 6e, or CO attack 6n could afford unstable products. If this was the case, we reasoned that the problems could be circumvented by replacing one of the CO ligands in 1a with a phosphito ligand .…”

“…Several studies have focused on the addition of “classical” nucleophiles to the arene ring of these manganese complexes. These nucleophiles include carbanion enolates, Grignard reagents, α-cyano- or α-nitrocarbanions, − diazo groups, and phosphonates . In contrast, a small number of investigations have used organometallic derivatives as nucleophiles …”

Preparation of o-bromobenzophenone derivatives from lithium diarylcuprate(I) reagents

“…Products were initially identified by comparison of their melting points with literature data and by the observation of characteristic peaks in their IR and UV spectra ( Table 1). 1 H NMR spectroscopic and analytical results of the unsymmetrically substituted benzophenone derivatives 5-8 are given in Table 2. The yields of the reactions were generally good and introduction of the bromo group into the aroyl chloride seemed to have little effect on the yield of the reaction.…”

“…1 A currently popular method for the synthesis of such unsymmetrical ketones, which avoids the formation of isomers, is the reaction of organometallic reagents with acid chlorides. 2 Recently Palladium(0) catalysts 3 and some elaborately prepared organocopper 4 or copper-zinc 5 reagents have been employed for this purpose.…”

“…However, due to their familiarity and relative ease of preparation, we initially considered the reaction of lithium diarylcuprate(I) reagents with ortho bromo-substituted aromatic acid chlorides as a possible means of synthesis of these derivatives. (Eqn [1]). …”