The Electronic Structure of V(CO)6. Why It Is Black

Gary F. Holland, Mark C. Manning, Donald E. Ellis, William C. Trogler*

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

41 Scopus citations


The stable free radical vanadium hexacarbonyl does not absorb appreciably below 25 000 cm-1 in dilute Solution or when isolated in N2 matrices at 15 K. In the solid State, however, V(CO)6 appears black due to a broad weak electronic absorption centered at 580 nm (17 250 cm-1). Nonempirical SCF-Xα-DV calculations predict an orbital energy scheme for V(CO)6 that is very similar to the 18e Systems V(CO)6- and Cr(CO)6. These calculations satisfactorily account for the ionization spectrum of V(CO)6 and its electronic absorption spectrum in dilute Solution. Furthermore, the electron-density distribution calculated for the highest occupied molecular orbital [d5(t2g5)] agrees well with that deduced in a previous EPR study. The t2g electrons reside on vanadium about 55% of the time and are about 45% delocalized onto the CO ligands. These data indicate extensive metal-CO π bonding. Single-molecule properties cannot explain the color of solid V(CO)6. A model based on the solid-state excitation process V(CO)6V(CO)6 (+hv) → [V(CO)6+] [V(CO)6-] is energetically reasonable on the basis of SCF-Xα-DV calculations. To test this conclusion, electronic spectra of V(CO)6/M(CO)6 [M = Cr, Mo, W] mixed crystals were measured. In these Systems the M(CO)6V(CO)6 (+hv) → [M(CO)6+] [V(CO)6-] excitation should occur at higher energy due to the greater ionization potentials of the M(CO)6 complexes compared to V(CO)6. In fact, the doped crystals are pale orange colored and absorb maximally at 475 nm.

Original languageEnglish (US)
Pages (from-to)2308-2314
Number of pages7
JournalJournal of the American Chemical Society
Issue number8
StatePublished - Mar 1983

ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry


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