Ancillary ligand effects upon dithiolene redox noninnocence in tungsten Bis(dithiolene) complexes

Yong Yan, Christopher Keating, Perumalreddy Chandrasekaran, Upul Jayarathne, Joel T. Mague, Serena Debeer, Kyle M. Lancaster, Stephen Sproules, Igor V. Rubtsov, James P. Donahue

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An expanded set of compounds of the type [W(S2C 2Me2)2L1L2]n (n = 0: L1 = L2 = CO, 1; L1 = L2 = CNtBu, 2; L1 = CO, L2 = carbene, 3; L 1 = CO, L2 = phosphine, 4; L1 = L2 = phosphine, 5. n = 2-: L1 = L2 = CN-, [6] 2-) has been synthesized and characterized. Despite isoelectronic formulations, the compound set reveals gradations in the dithiolene ligand redox level as revealed by intraligand bond lengths, υCCchelate, and rising edge energies in the sulfur K-edge X-ray absorption spectra (XAS). Differences among the terminal series members, 1 and [6]2-, are comparable to differences seen in homoleptic dithiolene complexes related by full electron transfer to/from a dithiolene-based MO. The key feature governing these differences is the favorable energy of the CO π* orbitals, which are suitably positioned to overlap with tungsten d orbitals and exert an oxidizing effect on both metal and dithiolene ligand via π-backbonding. The CN- π* orbitals are too high in energy to mix effectively with tungsten and thus leave the filled dithiolene π* orbitals unperturbed. This work shows how, and the degree to which, the redox level of a noninnocent ligand can be modulated by the choice of ancillary ligands(s).

Original languageEnglish (US)
Pages (from-to)6743-6751
Number of pages9
JournalInorganic Chemistry
Issue number11
StatePublished - Jun 3 2013
Externally publishedYes

All Science Journal Classification (ASJC) codes

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry


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