Ruthenium complexes of [2n]cyclophanes. A general synthesis of bis(.eta.6-[2n]cyclophane)ruthenium(II) compounds and related chemistry

Molecular Electrochemistry of Cyclophanes

“…14.6), albeit isolation of reduction products proved impossible [90,98]. The CV curve (supported by coulometric results) is consistent with three twoelectron reductions at increasingly negative potentials (peaks 1, 3, and 4), linked to first-order chemical steps.…”

“…The aromatic rings in [2.2]paracyclophane can easily attain the desired bent conformation [90] for g 4 -hapticity, which should be favorable for the reduction of complexes like 28. Indeed, the flexibility of the [2 n ]cyclophane in a series of complexes [68] governs the ease of reduction [90].…”

“…Indeed, the flexibility of the [2 n ]cyclophane in a series of complexes [68] governs the ease of reduction [90]. This is particularly true for bis(g 6 -[2.2]paracyclophane)ruthenium(II) (30) [90].…”

Synthesis and reactivity of [(η6-[32](1,3)Cyclophane)Mn(CO)3][BF4]

“…The increased electron density on the metal in 3 compared to 2 is evidenced by the shorter Mn-CO distances in 3. Although Boekelheide et al [7]. have reported that reaction of (6-hexamethylbenzene)-(g 4 -[2 2 ](1,4)cyclophane)ruthenium with hydrochloric acid gives (6-hexamethyl-benzene)(g 5 -3H- [2 2 ] (1,4)cyclophane)ruthenium(II) hydrogen dichloride, compound 3 apparently is the first example of preparing a [(g 5 -6H-[3 2 ](1,3)cyclophane)Mn(CO) 3 ] complex [15,16].…”

“…We also found that multi-bridged [3 n ]cyclophanes(n ¼ 3 [5] and 4 [6]) underwent photochemical reactions in solution to give polycyclic cage compounds with novel skeletons. Boekelheide et al [7] reported that the protonation of [(g 6 -hexamethylbenzene)(g 4 - [2 2 ](1,4) cyclophane)]ruthenium(0) gives a cyclophane ruthenium complex (A) containing a cyclohexadienyl anion deck. In an attempt to pursue further studies on thereactivity of the benzene deck of the cyclophane ligand, we envisioned that the cationic manganese complex of type 2 would be a good candidate because a variety of nucleophiles are known to add to the arene ring in (arene)Mn(CO) þ 3 to yield the corresponding cyclohexadienyl complex [8].…”