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Amphiphilic Dendrimers with Heteroleptic Bis([2,2′: 6′,2″]terpyridine)-Ruthenium(II) Cores

✍ Scribed by Derk Joester; Volker Gramlich; François Diederich

Publisher
John Wiley and Sons
Year
2004
Tongue
German
Weight
605 KB
Volume
87
Category
Article
ISSN
0018-019X

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✦ Synopsis

Abstract

A new series of dendrimers was assembled through formation of homo‐ and heteroleptic Ru^II^ complexes with [2,2′: 6′,2″]terpyridine ligands bearing hydrophilic and hydrophobic dendrons, with the aim to develop amphiphilic vectors for potential use in gene delivery (Scheme 1). The synthesis started with the preparation of the 4′‐(3,5‐dihalo‐4‐methoxyphenyl)‐[2,2′: 6′,2″]terpyridine ligands 1a,b via the Kröhnke pyridine synthesis (Scheme 2), followed by attachment of dendrons 10a–10f (Fig. 2) by Sonogashira cross‐coupling to give the dendritic ligands 11–16 (Schemes 3 and 4). Ligands were subsequently introduced into the coordination sphere of Ru^III^ to give the stable intermediates [Ru(11)Cl~3~] (24; Scheme 7) and [Ru(14)Cl~3~] (27; Scheme 8). These were transformed under reductive conditions into the heteroleptic complexes Ru(11)(13)~2~ (25) and Ru(13)(14)~2~ (29). Removal of the (tert‐butoxy)carbonyl (Boc) protecting groups in 25 and 29 then gave the desired amphiphilic dendrimers 26 (Scheme 7) and 30 (Scheme 8) with branchings of generations 0 and 1. Complex formation was analyzed by high‐resolution matrix‐assisted laser‐desorption‐ionization Fourier‐transform ion‐cyclotron‐resonance mass spectrometry (HR‐MALDI‐FT‐ICR‐MS), which provided spectra featuring unique fragment‐ion series and perfectly resolved isotope distribution patterns (Figs. 4 and 5). The preparation of homo‐ and heteroleptic complexes with terpyridine ligands bearing generation‐2 dendrons failed due to steric hindrance by the bulky wedges.

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