Accessibility navigation


Diphenylamine-substituted osmanaphthalyne complexes: structural, bonding, and redox properties of unusual donor–bridge–acceptor systems

Zhang, M.-X., Zhang, J., Jin, X., Sun, X., Yin, J., Hartl, F. and Liu, S. H. (2018) Diphenylamine-substituted osmanaphthalyne complexes: structural, bonding, and redox properties of unusual donor–bridge–acceptor systems. Chemistry - A European Journal, 24 (71). pp. 18998-19009. ISSN 0947-6539

[img] Text - Accepted Version
· Restricted to Repository staff only until 21 November 2019.

1MB

It is advisable to refer to the publisher's version if you intend to cite from this work. See Guidance on citing.

To link to this item DOI: 10.1002/chem.201804025

Abstract/Summary

Diarylamine-substituted osmanaphthalyne complexes that feature two redox centers linked by the rigid skeleton of the metallacycle (C^C+), specifically, [OsCl2(PPh3)2{(C^C+)NAr2}][BF4 ] (Ar=Ph (1 a), p-MeOPh (1 b)) and their open-ring precursors [OsHCl2(PPh3)2{(CC(PPh3 +)= CHPh)NR2}][BF4 ] (Ar=Ph (2 a), p-MeOPh (2 b)), were successfully synthesized and characterized by 1 H, 13C, and 31P NMR spectroscopy, ESI-MS, and elemental analysis. The solid-state molecular structures of complexes 1 a and 2 a were ascertained by single-crystal X-ray diffraction. The OsC bond length in both complexes 1 a and 2 a fell within the range reported for similar osmanaphthalynes and osmium carbyne complexes, respectively. The structural parameters determined for complex 1 a, which were successfully reproduced by theoretical calculations, point to a p-delocalized metallacycle structure. The purple color of compounds 1 a and b was explained by the diarylamine!Os(metallacycle) chargetransfer absorption in the visible region. The neutral, oneelectron-oxidized and one-electron-reduced states of compounds 1 a, b, and a reference complex that lacked the diarylamine substituent, [OsCl2(PPh3)2{(C^C+)}][BF4] (1’), were investigated by cyclic and square-wave voltammetry, UV/Vis/NIR spectroelectrochemistry, and DFT calculations. The spin density in singly oxidized complexes [1 a]+ and [1 b]+ predominantly resided on the aminyl segment, with osmium involvement controlled by the diphenylamine substitution. Spin density in stable, singly-reduced [1’] was distributed mainly over the osmanaphthalyne metallacycle.

Item Type:Article
Refereed:Yes
Divisions:Faculty of Life Sciences > School of Chemistry, Food and Pharmacy > Department of Chemistry
ID Code:80900
Publisher:Wiley-V C H Verlag GMBH

University Staff: Request a correction | Centaur Editors: Update this record

Page navigation