Stabilizing the elusive ortho-quinone/copper(I) oxidation state combination through p/p interaction in an isolated complex

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Journal of the American Chemical Society, 130 (46): 15230--15231 (2008)
DOI: 10.1021/ja804429v


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)



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