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Variation of the electron population by four units in the cluster series [(eta(5)-Cp ')(3)Mo3S4Co(L)](n+) (L = I, CO, PPh3, NO; n=0, 1)

Herbst, Konrad; Soderhjelm, Emma; Nordlander, Ebbe LU ; Dahlenburg, Lutz and Brorson, Michael (2007) In Inorganica Chimica Acta 360(8). p.2697-2703
Abstract
The versatility of cuboidal Mo3S4Co clusters for the preparation of complexes with different numbers of valence shell electrons (VSE) in the cluster is described. The reaction of the geometrically incomplete cuboidal cluster salt [(eta(5)-Cp')(3)Mo3S4][pts] (pts = p-toluenesulfonate) with one molar equivalent of [Co-2(CO)(8)] afforded almost quantitatively the electroneutral 60 VSE cluster [(eta(5)-Cp')(3)Mo3S4Co(CO)] (1), which previously has been prepared in low yield by Curtis et al. in autoclave syntheses [M.D. Curtis, U. Riaz, O.J. Curnow, J.W. Kampf, Organometallics 14 (1995) 5337]. Cluster 1 was also obtained in high yield by reaction of [(eta(5)-Cp')(3)Mo3S4][pts] with [(eta(5)-Cp*)Co(CO)(2)]. Reaction of... (More)
The versatility of cuboidal Mo3S4Co clusters for the preparation of complexes with different numbers of valence shell electrons (VSE) in the cluster is described. The reaction of the geometrically incomplete cuboidal cluster salt [(eta(5)-Cp')(3)Mo3S4][pts] (pts = p-toluenesulfonate) with one molar equivalent of [Co-2(CO)(8)] afforded almost quantitatively the electroneutral 60 VSE cluster [(eta(5)-Cp')(3)Mo3S4Co(CO)] (1), which previously has been prepared in low yield by Curtis et al. in autoclave syntheses [M.D. Curtis, U. Riaz, O.J. Curnow, J.W. Kampf, Organometallics 14 (1995) 5337]. Cluster 1 was also obtained in high yield by reaction of [(eta(5)-Cp')(3)Mo3S4][pts] with [(eta(5)-Cp*)Co(CO)(2)]. Reaction of [(eta(5)-Cp')(3)Mo3S4][pts] with two molar equivalents of [Co(I)(CO)(3)(PPh3)] led to a complex mixture of products, of which the electron deficient 58 VSE cluster salt [(eta(5)-Cp')(3)Mo3S4Co(I)[Co(I)(3)(thf)] ([2][Co(I)(3)(thf)]) was isolated as single crystals. In the crystal structures of 1 and [2][Co(I)(3)(thf)], the Co-Mo bond lengths are almost identical, indicating a delocalization of the electron deficiency in [2](+). The reduced form of [2](+), [(eta(5)-Cp ')(3)Mo3S4Co(I)] (2), was prepared by oxidative substitution of the carbonyl ligand in 2 by I-2. Further reactions of 2 with PPh3 and NO leading to the 60 and 61 VSE cluster complexes [(eta(5)-Cp')(3)Mo3S4Co(PPh3)](3) and [(eta(5)-Cp')(3)Mo3S4Co(NO)] (4), respectively, enabled the preparation of Mo3S4Co clusters in altogether four different oxidation states. (Less)
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organization
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Contribution to journal
publication status
published
subject
keywords
cuboidal, cluster, molybdenum, cobalt, electron deficiency
in
Inorganica Chimica Acta
volume
360
issue
8
pages
2697 - 2703
publisher
Elsevier
external identifiers
  • wos:000247165200023
  • scopus:34247463628
ISSN
0020-1693
DOI
10.1016/j.ica.2007.01.014
language
English
LU publication?
yes
id
10332b8c-ae1a-43ba-86c7-d29e77c2fb7e (old id 659524)
date added to LUP
2007-12-11 13:46:22
date last changed
2017-01-01 07:18:47
@article{10332b8c-ae1a-43ba-86c7-d29e77c2fb7e,
  abstract     = {The versatility of cuboidal Mo3S4Co clusters for the preparation of complexes with different numbers of valence shell electrons (VSE) in the cluster is described. The reaction of the geometrically incomplete cuboidal cluster salt [(eta(5)-Cp')(3)Mo3S4][pts] (pts = p-toluenesulfonate) with one molar equivalent of [Co-2(CO)(8)] afforded almost quantitatively the electroneutral 60 VSE cluster [(eta(5)-Cp')(3)Mo3S4Co(CO)] (1), which previously has been prepared in low yield by Curtis et al. in autoclave syntheses [M.D. Curtis, U. Riaz, O.J. Curnow, J.W. Kampf, Organometallics 14 (1995) 5337]. Cluster 1 was also obtained in high yield by reaction of [(eta(5)-Cp')(3)Mo3S4][pts] with [(eta(5)-Cp*)Co(CO)(2)]. Reaction of [(eta(5)-Cp')(3)Mo3S4][pts] with two molar equivalents of [Co(I)(CO)(3)(PPh3)] led to a complex mixture of products, of which the electron deficient 58 VSE cluster salt [(eta(5)-Cp')(3)Mo3S4Co(I)[Co(I)(3)(thf)] ([2][Co(I)(3)(thf)]) was isolated as single crystals. In the crystal structures of 1 and [2][Co(I)(3)(thf)], the Co-Mo bond lengths are almost identical, indicating a delocalization of the electron deficiency in [2](+). The reduced form of [2](+), [(eta(5)-Cp ')(3)Mo3S4Co(I)] (2), was prepared by oxidative substitution of the carbonyl ligand in 2 by I-2. Further reactions of 2 with PPh3 and NO leading to the 60 and 61 VSE cluster complexes [(eta(5)-Cp')(3)Mo3S4Co(PPh3)](3) and [(eta(5)-Cp')(3)Mo3S4Co(NO)] (4), respectively, enabled the preparation of Mo3S4Co clusters in altogether four different oxidation states.},
  author       = {Herbst, Konrad and Soderhjelm, Emma and Nordlander, Ebbe and Dahlenburg, Lutz and Brorson, Michael},
  issn         = {0020-1693},
  keyword      = {cuboidal,cluster,molybdenum,cobalt,electron deficiency},
  language     = {eng},
  number       = {8},
  pages        = {2697--2703},
  publisher    = {Elsevier},
  series       = {Inorganica Chimica Acta},
  title        = {Variation of the electron population by four units in the cluster series [(eta(5)-Cp ')(3)Mo3S4Co(L)](n+) (L = I, CO, PPh3, NO; n=0, 1)},
  url          = {http://dx.doi.org/10.1016/j.ica.2007.01.014},
  volume       = {360},
  year         = {2007},
}