Coordinating Tectons: Bipyridyl Terminated Allenylidene Complexes

M.P. Cifuentes, M.G. Humphrey, George Koutsantonis, Nigel Lengkeek, S. Petrie, V. Sanford, Philip Schauer, Brian Skelton, R. Stranger, Allan White

Research output: Contribution to journalArticle

24 Citations (Scopus)

Abstract

A series of complexes with T-conjugated carbon chains terminated by bipyridyl moieties has been prepared. These allenylidene complexes were derived from 9-hydroxy-9-ethynyl-4,5-diazafluorene, the preparation of which is reported; the new allenylidene complexes are highly colored with the cumulated carbon chain terminating in a bipyridyl unit providing a site for further coordination. The synthesis, characterization, and X-ray structure determination of tratis-[MCl(P boolean AND P)(2)=C=C=(4,5-diazafluoren-9-yl)]PF6 (M = Ru, P boolean AND P = bis(diphenylphosphino)methane (dppm), 1,2-bis(diphenylphosphino)ethane (dppe), 1,2-bis(dimethylphosphino)ethane (dmpe); M = Os, P boolean AND P = dppm) are described. The effect of the variation in metal and ligand on electronic and electrochemical characteristics of these complexes has been investigated by using UV-vis, solution electrochemistry, and a combination of these techniques in spectroelectrochemical experiments. DFT calculations have been performed on trans-[RuCl (P boolean AND P)(2) =C=C=(4,5-diazafluoren-9-yl)](q) (P boolean AND P = dppm, bis(dimethylphosphino)methane (dmpm); q = -1, 0, +1, +2) and subsequently solvent-corrected calculations with use of COSMO were also undertaken to examine the nature of electronic transitions in various oxidation states.
Original languageEnglish
Pages (from-to)1716-1726
JournalOrganometallics
Volume27
Issue number8
DOIs
Publication statusPublished - 2008

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