The synthesis of dipridyl- and 1,10-phenanthrolylferrocenes and bis-N,N′-(2,2′-dipyridyl(6-ferrocenyl-N,N′-2,2′-dipyridyl))ruthenium dichloride

Abstract

. Can. J. Chem. 68, 2212Chem. 68, (1990. Ferrocenyldipyridyls and ferrocenyl-o-phenanthrolines have been synthesized by the direct reaction of lithioferrocenes with the appropriate dipyridine or 1,IO-phenanthroline. The spectroscopic properties of these potential new ligands are described and the synthesis of bis-2,2'-dipyridyl(6-ferrocenyl-2,2'-dipyridyl)ruthenium dichloride, 8, in its hydrated form is reported.

Direct C–C Coupling of Ferrocenyllithium and Azaheterocycles by Nucleophilic Substitution of Hydrogen – Synthesis of Mono‐ and 1,1′‐Diazinylferrocenes

“…More recently, 2,2Ј-bipyridine and 1,10-phenanthroline derivatives were also synthesized according to this method (yields 20-40 %). [15] According to the mechanism accepted for nucleophilic aromatic substitution of hydrogen, this reaction can be considered as a two-step "addition-elimination" process giving 4a-k as the final products (Scheme 1 and Table 1). In the first reversible step, unstable intermediates A having a dihydroazine structure are generated under an atmosphere of argon.…”

“…In the absence of a dehydrogenating agent, σ H adduct A can undergo side reactions. [12] The general scheme outlined in Scheme 1 has not been considered as an S N H process in the cited papers, [13][14][15] in neither case was the oxidizer specially chosen. In our opinion, this is the main cause for poor yields.…”

“…In our opinion, this is the main cause for poor yields. As for the oxidation of the σ H adducts, it occurred spontaneously [13][14][15] because of the contact of A with air. Thus, a natural oxidizer, viz.…”

“…[16] Diethyl ether is the solvent of choice for the synthesis of monosubstituted azinylferrocenes. The use of DDQ and diethyl ether at room temperature allowed us to shorten the reaction time from 16 h [13][14][15] to 30 min. It was found that the reaction with the use of bromoferrocene as the starting material instead of ferrocene [13][14][15] affords only pure monolithiation product 2, as evidenced by the absence of even trace amounts of disubstituted ferrocenes among the reaction products.…”

“…In addition, we managed to increase the yields of known [13][14][15] ferrocene derivatives of pyridine, quinoline, 2,2Ј-bipyridyl, and 1,10-phenanthroline. Compounds 4a-k are orange-red solids (λ max ≈ 450 nm in methanol).…”