5 years ago

Cationic Copper Hydride Clusters Arising from Oxidation of (Ph3P)6Cu6H6

Cationic Copper Hydride Clusters Arising from Oxidation of (Ph3P)6Cu6H6
Xiaodong Yin, Shuo Liu, Daniel W. Paley, Jack R. Norton, Michael S. Eberhart, Michelle C. Neary
Transfer of the first electron from (Ph3P)6Cu6H6 to Cp*2Fe+ is fast (k > 106 L·mol–1·s–1). Transfer of a second electron to the same oxidant has a much lower thermodynamic driving force and is considerably slower, with k = 9.29(4) × 103 L·mol–1·s–1. The second oxidation leads to the formation of [(Ph3P)6Cu6H5]+. The structure of [(Ph3P)6Cu6H5]+ has been confirmed by its conversion back to (Ph3P)6Cu6H6 and by microanalysis; X-ray diffraction shows that the complex is a bitetrahedron in the solid state. [(Ph3P)6Cu6H5]+ can also be prepared by treating (Ph3P)6Cu6H6 with MeOTf. With less than 1 equiv of Cp*2Fe+ as oxidant, (Ph3P)6Cu6H6 gives [(Ph3P)7Cu7H6]+ as the major product; X-ray diffraction shows a Cu6 octahedron with one face capped by an additional Cu. [(Ph3P)7Cu7H6]+ can also be prepared by treating (Ph3P)6Cu6H6 with [Cu(CH3CN)4]+ (along with 1 equiv of Ph3P), and can be converted back to (Ph3P)6Cu6H6 with base/H2.

Publisher URL: http://dx.doi.org/10.1021/jacs.7b02183

DOI: 10.1021/jacs.7b02183

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