TY - JOUR
T1 - Coordinating tectons
T2 - Bipyridyl terminated allenylidene complexes
AU - Cifuentes, Marie P.
AU - Humphreys, Mark G.
AU - Koutsantonis, George A.
AU - Lengkeek, Nigel A.
AU - Petrie, Simon
AU - Sanford, Vanessa
AU - Schauer, Phil A.
AU - Skelton, Brian W.
AU - Stranger, Robert
AU - White, Allan H.
PY - 2008/4/28
Y1 - 2008/4/28
N2 - A series of complexes with π-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 trans-[MCl(P∩P)2=C=C=(4,5-diazafluoren-9-yl)]PF6 (M = Ru, P∩P = bis(diphenylphosphino)methane (dppm), 1,2- bis(diphenylphosphino)ethane (dppe), 1,2-bis(dimethylphosphino)ethane (dmpe); M = Os, P∩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∩P)2 =C=C=(4,5-diazafluoren-9-yl) q (P∩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.
AB - A series of complexes with π-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 trans-[MCl(P∩P)2=C=C=(4,5-diazafluoren-9-yl)]PF6 (M = Ru, P∩P = bis(diphenylphosphino)methane (dppm), 1,2- bis(diphenylphosphino)ethane (dppe), 1,2-bis(dimethylphosphino)ethane (dmpe); M = Os, P∩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∩P)2 =C=C=(4,5-diazafluoren-9-yl) q (P∩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.
UR - http://www.scopus.com/inward/record.url?scp=43249102429&partnerID=8YFLogxK
U2 - 10.1021/om700824g
DO - 10.1021/om700824g
M3 - Article
SN - 0276-7333
VL - 27
SP - 1716
EP - 1726
JO - Organometallics
JF - Organometallics
IS - 8
ER -