Journal
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
Volume 139, Issue 23, Pages 7685-7688Publisher
AMER CHEMICAL SOC
DOI: 10.1021/jacs.7b02183
Keywords
-
Categories
Funding
- Department of Energy [DE-FG01-97ER14807]
- National Science Foundation [DGE-11-44155]
Ask authors/readers for more resources
Transfer of the first electron from (Ph3P)(6)Cu6H6 to Cp*Fe-2(+) is fast (k > 10(6) 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) X 10(3) L.mol(-1)s(-1). The second oxidation leads to the formation of [(Ph3P)(6)Cu6H5](+). The structure of [(Ph3P)(6)Cu6H5](+) has been confirmed by its conversion back to (Ph3P)(6)Cu6H6 and by microanalysis; X-ray diffraction shows that the complex is a bitetrahedron in the solid state. [(Ph3P)(6)Cu6H5](+) can also be prepared by treating (Ph3P)(6)Cu6H6 with MeOTf. With less than 1 equiv of Cp*Fe-2(+) as oxidant, (Ph3P)(6)Cu6H6 gives [(Ph3P)(7)Cu7H6](+) as the major product; X-ray diffraction shows a Cu-6 octahedron with one face capped by an additional Cu. [(Ph3P)(7)Cu7H6](+) can also be prepared by treating (Ph3P)(6)Cu6H6 with [Cu(CH3CN)(4)](+) (along with 1 equiv of Ph3P), and can be converted back to (Ph3P)(6)Cu6H6 with base/H-2.
Authors
I am an author on this paper
Click your name to claim this paper and add it to your profile.
Reviews
Recommended
No Data Available