Linked Life Data

18975889

Source:http://linkedlifedata.com/resource/pubmed/id/18975889

Statements in which the resource exists as a subject.
PredicateObject
rdf:type
lifeskim:mentions
pubmed:issue
47
pubmed:dateCreated
2009-2-20
pubmed:abstractText
DFT calculations, using the PW91, OLYP, and B3LYP functionals, have provided some of the first estimates of the relative energies of the Ni(I) and Ni(II) ligand anion radical states of hydroporphyrin complexes. Although the three functionals chosen sometimes yield discordant results, the results of this study are essentially functional-independent. For isobacteriochlorin derivatives, our calculations predict that the Ni(I) state may be favored by 0.5 eV or more, relative to the ligand anion radical state. For other hydroporphyrins, however, electrochemical studies indicate a much finer balance, which may be tipped one way or the other, depending on the substituents. DFT calculations nicely capture these rather subtle substituent effects. In particular, our results support and extend Bruckner and co-workers' finding (from electrochemical studies) that the most rigid, strongly ruffled nickel chlorins prefer to reduce on the macrocycle, whereas their more flexible congeners undergo metal-centered reduction.
pubmed:language
eng
pubmed:journal
pubmed:citationSubset
IM
pubmed:chemical
pubmed:status
MEDLINE
pubmed:month
Nov
pubmed:issn
1520-6106
pubmed:author
pubmed:issnType
Print
pubmed:day
27
pubmed:volume
112
pubmed:owner
NLM
pubmed:authorsComplete
Y
pubmed:pagination
15158-73
pubmed:meshHeading
pubmed:year
2008
pubmed:articleTitle
DFT at its best: metal- versus ligand-centered reduction in nickel hydroporphyrins.
pubmed:affiliation
Department of Chemistry, University of Tromsø, 9037 Tromsø, Norway.
pubmed:publicationType
Journal Article, Research Support, Non-U.S. Gov't