Linked Life Data

17346040

Source:http://linkedlifedata.com/resource/pubmed/id/17346040

Statements in which the resource exists as a subject.
PredicateObject
rdf:type
lifeskim:mentions
pubmed:issue
7
pubmed:dateCreated
2007-3-26
pubmed:abstractText
Substitution reactions at the nickel site of the cubane-type cluster [(Ph3P)NiFe3S4(LS3)]2- (2) have been investigated in the course of a synthetic approach to the C-clusters of CODH. Reaction of 2 with RS- or toluene-3,4-dithiolate affords [(RS)NiFe3S4(LS3)]3- (R = Et (5), H (6)) or [(tdt)NiFe3S4(LS3)]3- (7), demonstrating that anionic sulfur ligands can be bound at the NiII site. Clusters 5 and 6 contain tetrahedral Ni(micro3-S)3(SR) sites. Cluster 7 is of particular interest because it includes a cubanoid NiFe3(micro2-S)(micro3-S)3 core and an approximately planar Ni(tdt)(micro3-S)2 unit. The cubanoid structure is found in all C-clusters, and an NiS4-type unit has been reported in C. hydrogenoformans CODH. Clusters 5/6 are formulated to contain the core [NiFe3S4]1+ identical with Ni2+ (S = 1) + [Fe3S4]1- (S = 5/2) and 7 the core [NiFe3S4]2+ identical with Ni2+ (S = 0) + [Fe3S4]0 (S = 2) on the basis of structure, 57Fe isomer shifts, and 1H NMR isotropic shifts. Also reported are [(EtS)CuFe3S4(LS3)]3- (9) and [Fe4S4(LS3)(tdt)]3- (11). The structures of 5-7, 9, and 11 are presented. Cluster 11, with a five-coordinate Fe(tdt)(micro3-S)3 site, provides a clear structural contrast with 7, which is currently the closest approach to a C-cluster but lacks the exo iron atom found in the NiFe4S4,5 cores of the native clusters. (CODH = carbon monoxide dehydrogenase, LS3 = 1,3,5-tris((4,6-dimethyl-3-mercaptophenyl)thio)-2,4,6-tris(p-tolylthio)benzene(3-), tdt = toluene-3,4-dithiolate).
pubmed:grant
pubmed:language
eng
pubmed:journal
pubmed:citationSubset
IM
pubmed:chemical
pubmed:status
MEDLINE
pubmed:month
Apr
pubmed:issn
0020-1669
pubmed:author
pubmed:issnType
Print
pubmed:day
2
pubmed:volume
46
pubmed:owner
NLM
pubmed:authorsComplete
Y
pubmed:pagination
2691-9
pubmed:dateRevised
2007-12-3
pubmed:meshHeading
pubmed:year
2007
pubmed:articleTitle
Sulfur ligand substitution at the nickel(II) sites of cubane-type and cubanoid NiFe3S4 clusters relevant to the C-clusters of carbon monoxide dehydrogenase.
pubmed:affiliation
Department of Chemistry and Chemical Biology, Harvard University, Cambridge, Massachusetts 02138, USA.
pubmed:publicationType
Journal Article, Research Support, Non-U.S. Gov't, Research Support, N.I.H., Extramural