Linked Life Data

19860456

Source:http://linkedlifedata.com/resource/pubmed/id/19860456

Statements in which the resource exists as a subject.
PredicateObject
rdf:type
lifeskim:mentions
pubmed:issue
23
pubmed:dateCreated
2009-11-30
pubmed:abstractText
The spectroscopic features of a series of oxalate bridged complexes [((t)BuCO(2))(3)MM](2)-mu(2)-O(2)CCO(2) (where MM = Mo(2), MoW, and W(2)) in their neutral and singly oxidized (mixed valence) states are examined as a function of temperature and solvent. A large degree of electronic coupling between the two MM centers is evident, principally involving the MM delta orbitals mediated by the oxalate bridge pi* orbital. In the oxidized states these mixed valence ions show solvent independent intervalence charge transfer (alternatively termed charge resonance) bands, consistent with assignment to Class III (or electronically delocalized) within the Robin-Day classification scheme. In both the neutral and oxidized states these complexes also show an intense metal-to-ligand charge-transfer (MLCT) transition, involving the lowest unoccupied molecular orbital (LUMO) of the bridge. The solvent and temperature dependence of this transition is also reported along with an inspection and simulation of the vibronic features, which are notably altered when switching between the neutral and the mixed valence states as well as with variation of the nature of the MM unit. Collectively, these observations allow us to comment on the validity and limitations of current theories dealing with mixed valence ions that have hitherto ignored the information that can be gained from MLCT transitions.
pubmed:language
eng
pubmed:journal
pubmed:status
PubMed-not-MEDLINE
pubmed:month
Dec
pubmed:issn
1520-510X
pubmed:author
pubmed:issnType
Electronic
pubmed:day
7
pubmed:volume
48
pubmed:owner
NLM
pubmed:authorsComplete
Y
pubmed:pagination
10954-71
pubmed:year
2009
pubmed:articleTitle
Oxalate bridged MM (MM = Mo2, MoW, and W2) quadruply bonded complexes as test beds for current mixed valence theory: looking beyond the intervalence charge transfer transition.
pubmed:affiliation
Department of Chemistry, The Ohio State University, Columbus, Ohio 43210, USA.
pubmed:publicationType
Journal Article