The copper(I) diphosphine o-quinone heterodinuclear compd. [(PhenQ)Cu(dppf)][BF4] (PhenQ = 9,10-phenanthrenequinone dppf = 1,1'-bis(diphenylphosphino)ferrocene) was identified structurally and spectroscopically (NMR, IR, UV-vis) as a copper(I) complex of a completely unreduced ortho-quinone. Crystallog. and DFT calcn. results suggest that this stabilization of a hitherto elusive arrangement is partially owed to intramol. p/p interactions phenyl/PhenQ. Intermol. PhenQ/PhenQ p stacking is also obsd. in the crystal. According to DFT calcns., the p interactions are responsible for the considerably distorted coordination geometry at Cu(I) with one short and one longer Cu-O and Cu-P bond, resp., and with bond angles at copper ranging from 99° to 133°. Electrochem. redn. proceeds reversibly at low temps. to yield an EPR spectroscopically characterized semiquinone-copper(I) species. [on SciFinder(R)]
%0 Journal Article
%1 Roy.2008
%A Roy, Sayak
%A Sarkar, Biprajit
%A Bubrin, Denis
%A Niemeyer, Mark
%A Zalis, Stanislav
%A Lahiri, Goutam Kumar
%A Kaim, Wolfgang.
%D 2008
%J Journal of the American Chemical Society
%K complex complex;mol copper diphenylphosphinoferrocene monovalent ortho phenanthrenequinone prepn quinone structure structure;crystal
%N 46
%P 15230--15231
%R 10.1021/ja804429v
%T Stabilizing the elusive ortho-quinone/copper(I) oxidation state combination through p/p interaction in an isolated complex
%V 130
%X The copper(I) diphosphine o-quinone heterodinuclear compd. [(PhenQ)Cu(dppf)][BF4] (PhenQ = 9,10-phenanthrenequinone dppf = 1,1'-bis(diphenylphosphino)ferrocene) was identified structurally and spectroscopically (NMR, IR, UV-vis) as a copper(I) complex of a completely unreduced ortho-quinone. Crystallog. and DFT calcn. results suggest that this stabilization of a hitherto elusive arrangement is partially owed to intramol. p/p interactions phenyl/PhenQ. Intermol. PhenQ/PhenQ p stacking is also obsd. in the crystal. According to DFT calcns., the p interactions are responsible for the considerably distorted coordination geometry at Cu(I) with one short and one longer Cu-O and Cu-P bond, resp., and with bond angles at copper ranging from 99° to 133°. Electrochem. redn. proceeds reversibly at low temps. to yield an EPR spectroscopically characterized semiquinone-copper(I) species. [on SciFinder(R)]
@article{Roy.2008,
abstract = {The copper(I) diphosphine o-quinone heterodinuclear compd. [(PhenQ)Cu(dppf)][BF4] (PhenQ = 9,10-phenanthrenequinone dppf = 1,1'-bis(diphenylphosphino)ferrocene) was identified structurally and spectroscopically (NMR, IR, UV-vis) as a copper(I) complex of a completely unreduced ortho-quinone. Crystallog. and DFT calcn. results suggest that this stabilization of a hitherto elusive arrangement is partially owed to intramol. \textgreek{p}/\textgreek{p} interactions phenyl/PhenQ. Intermol. PhenQ/PhenQ \textgreek{p} stacking is also obsd. in the crystal. According to DFT calcns., the \textgreek{p} interactions are responsible for the considerably distorted coordination geometry at Cu(I) with one short and one longer Cu-O and Cu-P bond, resp., and with bond angles at copper ranging from 99° to 133°. Electrochem. redn. proceeds reversibly at low temps. to yield an EPR spectroscopically characterized semiquinone-copper(I) species. [on SciFinder(R)]},
added-at = {2019-07-15T13:41:23.000+0200},
author = {Roy, Sayak and Sarkar, Biprajit and Bubrin, Denis and Niemeyer, Mark and Zalis, Stanislav and Lahiri, Goutam Kumar and Kaim, Wolfgang.},
biburl = {https://puma.ub.uni-stuttgart.de/bibtex/2d6fb1a22f51d470b4ac79022d183eba1/b_schwederski},
doi = {10.1021/ja804429v},
interhash = {382d07f2a8d2fc9a00aa6482d87de4a1},
intrahash = {d6fb1a22f51d470b4ac79022d183eba1},
issn = {0002-7863},
journal = {Journal of the American Chemical Society},
keywords = {complex complex;mol copper diphenylphosphinoferrocene monovalent ortho phenanthrenequinone prepn quinone structure structure;crystal},
number = 46,
pages = {15230--15231},
timestamp = {2019-07-15T11:42:10.000+0200},
title = {Stabilizing the elusive ortho-quinone/copper(I) oxidation state combination through \textgreek{p}/\textgreek{p} interaction in an isolated complex},
volume = 130,
year = 2008
}
