Carbon-rich cyclopentadienyl ruthenium allenylidene complexes

Susanne Spörler,Andreas R Waterloo,Eike Hübner,Nicolai Burzlaff,Rik R Tykwinski,Frank Strinitz,Maximilian Dürr,Philipp Rodehutskors,Lisa Müller,Ivana Ivanović-Burmazović

doi:10.1039/c5nj03556b

Susanne Spörler, Andreas R Waterloo + Show 8 more

Open Access

https://doi.org/10.1039/c5nj03556b

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Abstract

Ruthenium allenylidene complexes based on carbon-rich polyaromatic moieties have been synthesized with interesting intermolecular π-interactions.

Highlights

In recent years, there has been great interest in bringing metal complexes in close contact with single-wall carbon nanotubes (SWCNTs)
The synthesis of the allenylidene complexes followed the procedure first reported by Selegue[52] by using the corresponding propargyl alcohols as building blocks. 10-Ethynyl-10-hydroxyanthracen-9-one (AO), 13-ethynyl-13-hydroxypentacen-6-one (PCO), 1-phenyl-1-(pyren1-yl)prop-2-yn-1-ol (PyrPh), 9-ethynyl-9H-fluoren-9-ol (FN) and 6-ethynyl-6H-benzo[cd]pyren-6-ol (BPyr) have been chosen as starting materials
A shoulder in the Job’s plot of 5 at w = 0.8 might indicate the presence of 2 : 1 pyrene : complex adduct species. To back these titration results, we investigated the aggregation of the complexes 2 and 5 with pyrene via cryospray-ionisation mass spectrometry (CSI-MS)

Summary

Introduction

There has been great interest in bringing metal complexes in close contact with single-wall carbon nanotubes (SWCNTs). Ruthenium allenylidene complexes with carbon-rich polyaromatic moieties have been synthesized by using [RuCl(Z5-C5H5)(PPh3)2] (Z5-C5H5 = cyclopentadienyl) as a precursor and the propargyl alcohols 10-ethynyl-10-hydroxyanthracen-9-one (ACO), 13-ethynyl-13-hydroxypentacen-6-one (PCO), 1-phenyl-1(pyren-1-yl)prop-2-yn-1-ol (PyrPh), 9-ethynyl-9H-fluoren-9-ol (FN) and 6-ethynyl-6H-benzo[cd]pyren-6-ol (BPyr) as ligands. The resulting cationic allenylidene complexes, [Ru(Z5-C5H5)(QCQCQ(AO))(PPh3)2]PF6 (1), [Ru(Z5-C5H5)(QCQCQ(PCO))(PPh3)2]PF6 (2), [Ru(Z5-C5H5)(QCQCQ(PyrPh))(PPh3)2]PF6 (3), [Ru(Z5-C5H5)(QCQCQ(FN))(PPh3)2]PF6 (4), and [Ru(Z5-C5H5)(QCQCQ(BPyr))(PPh3)2]PF6 (5) show interesting intermolecular p-interactions in the solid-state structure as well as solution state complexation with pyrene (documented by Job’s plots experiments).

Results

Conclusion