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Magnetic circular dichroism and electronic structure of [Re2X4(PMe3)4]+ (X = Cl, Br)
Diana Habel-Rodriguez1, Frederic Poineau, Erik V Johnstone
1Department of Chemistry and Chemical Biology, The University of New Mexico , MSC03 2060, 1 University of New Mexico, Albuquerque, New Mexico 87131-0001, United States.
Abstract:
Magnetic circular dichroism (MCD) and electronic absorption spectroscopies have been used to probe the electronic structure of the classical paramagnetic metal-metal-bonded complexes [Re2X4(PMe3)4](+) (X = Cl, Br). A violation of the MCD sum rule is observed that indicates the presence of ground-state contributions to the MCD intensity. The z-polarized δ → δ* band in the near-IR is formally forbidden in MCD but gains intensity through a combination of ground- and excited-state mechanisms to yield a positive C term.
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