Regioselective Synthesis and Characterization of Multinuclear Convex‐Bound Ruthenium‐[n]Cycloparaphenylene (n=5 and 6) Complexes

Abstract

Mono‐ and multinuclear complexes of ruthenium and [n]cycloparaphenylene (CPP, n=5 and 6) were synthesized in excellent yields through ligand exchange of the cationic complex [(Cp)Ru(CH3CN)3](PF6) with CPP. In the multinuclear complexes, ruthenium selectively coordinated to alternate paraphenylene units to give bis‐ and tris‐coordinated Ru complexes for [5] and [6]CPPs, respectively. Single‐crystal X‐ray analysis revealed the Ru was coordinated with η6‐hapticity on the convex surface of CPP.

Microwave‐Assisted Synthesis and Transformations of Cationic CpRu(II)(naphthalene) and CpRu(II)(naphthoquinone) Complexes

“…Thus, naphthalene substitution in 2 by arenes, phosphines, acetonitrile, amines takes place under mild conditions and can be accelerated by visible light. [20,22,[25][26][27][28][29][30][31][32] The microwave-mediated substitution of Cp for an arene ligand was extended to the preparation of a number of CpRu(arene) + complexes (Scheme 3).…”

Synthesis and metalation of polycatechol nanohoops derived from fluorocycloparaphenylenes

“…Thus far, only two metal-coordinating motifs have been established in CPPs: (1) the h 6 -coordination of metals to CPP phenylene rings, and (2) the chelation of metal cations to CPP-embedded 2,2 ′bipyridyl groups. Organometallic fragments such as M(CO) 3 (M = Cr, Mo, W) 17 and [M(Cp)] + (M = Ru) 18,19 have been shown to bind CPP phenylene rings in a face-on fashion, generating h 6complexes. In addition, 2,2 ′ -bipyridyl-embedded CPPs have been shown to chelate rstand second-row transition metals (M = Fe 2+ , Ru 2+ , Pd 2+ ).…”

Synthesis of a Substituted [10]Cycloparaphenylene through [2+2+2] Cycloaddition

“…In recent years, different strategies were explored to introduce manifold substituents and substitutional pattern to CPPs (Figure 1). [2,4,5–8] Two major approaches can be distinguished: The post functionalization of non‐substituted CPPs [9–12] and the introduction of substituents within the first building blocks [13–15] . The first principally offers the largest flexibility as unsubstituted CPPs are modified in the last step(s) of their synthesis.…”

“… Summary of strategies to access for substituted CPPs, classified by their synthetic methodology [5–20] …”