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Reactivity of triruthenium thiophyne and furyne clusters: competitive S-C and P-C bond cleavage reactions and the generation of highly unsymmetrical alkyne ligands

Uddin, Md. Nazim; Begum, Noorjahan; Hassan, Mohammad R.; Hogarth, Graeme; Kabir, Shariff E.; Miah, Md. Arzu; Nordlander, Ebbe LU and Tocher, Derek A. (2008) In Dalton Transactions p.6219-6230
Abstract
The synthesis and reactivity of the thiophyne and furyne clusters [Ru-3(CO)(7)(mu-dppm)(mu(3)-eta(2)-C4H2E){mu-P(C4H3E)(2)}(mu-H)] (E = S, O) is reported. Addition of P(C4H3E)(3) to [Ru-3(CO)(10)(mu-dppm)] (1) at room temperature in the presence of Me3NO gives simple substitution products [Ru-3(CO)(9)(mu-dppm)-P(C4H3E)(3)}] (E = S, 2; E = O, 3). Mild thermolysis in the presence of further Me3NO affords the thiophyne and furyne complexes [Ru-3(CO)(7)(mu-dppm)(mu(3)-eta(2)-C4H2E){mu-P(C4H3E)(2)}(mu-H)] (E = S, 4; E = O, 6) resulting from both carbon-hydrogen and carbon-phosphorus bond activation. In each the C4H2E (E = S, O) ligand donates 4-electrons to the cluster and the rings are tilted with respect to the m-dppm and the... (More)
The synthesis and reactivity of the thiophyne and furyne clusters [Ru-3(CO)(7)(mu-dppm)(mu(3)-eta(2)-C4H2E){mu-P(C4H3E)(2)}(mu-H)] (E = S, O) is reported. Addition of P(C4H3E)(3) to [Ru-3(CO)(10)(mu-dppm)] (1) at room temperature in the presence of Me3NO gives simple substitution products [Ru-3(CO)(9)(mu-dppm)-P(C4H3E)(3)}] (E = S, 2; E = O, 3). Mild thermolysis in the presence of further Me3NO affords the thiophyne and furyne complexes [Ru-3(CO)(7)(mu-dppm)(mu(3)-eta(2)-C4H2E){mu-P(C4H3E)(2)}(mu-H)] (E = S, 4; E = O, 6) resulting from both carbon-hydrogen and carbon-phosphorus bond activation. In each the C4H2E (E = S, O) ligand donates 4-electrons to the cluster and the rings are tilted with respect to the m-dppm and the phosphido-bridged open triruthenium unit. Heating 4 at 80 degrees C leads to the formation of the ring-opened cluster [Ru-3(CO)(5)(mu-CO)(mu-dppm)(mu(3)-eta(3)-SC4H3){mu-P(C4H3S)(2)}] (5) resulting from carbon-sulfur bond scission and carbon- hydrogen bond formation and containing a ring-opened mu(3)-eta(3)-1-thia-1,3-butadiene ligand. In contrast, a similar thermolysis of 3 affords the phosphinidene cluster [Ru-3(CO)(7)(mu-dppm)(mu(3)-eta(2)-C4H2O){mu(3)-P(C4H3O)}] (7) resulting from a second phosphorus-carbon bond cleavage and (presumably) elimination of furan. Treatment of 4 and 6 with PPh3 affords the simple phosphine-substituted products [Ru-3(CO)(6)(PPh3)(mu-ppm)(mu(3)-eta(2)-C4H2E){mu-P(C4H3E)(2)}(mu-H)] (E = S, 8; E = O, 9). Both thiophyne and furyne clusters 4 and 6 readily react with hydrogen bromide to give [Ru-3(CO)(6)Br(mu-Br)(mu-dppm)(mu(3)-eta(2)-eta(1)-C4H2E){mu-P(C4H3E)(2) }(mu-H)] (E = S, 10; E = O, 11) containing both terminal and bridging bromides. Here the alkynes bind in a highly unsymmetrical manner with one carbon acting as a bridging alkylidene and the second as a terminally bonded Fisher carbene. As far as we are aware, this binding mode has only previously been noted in ynamine complexes or those with metals in different oxidation states. The crystal structures of seven of these new triruthenium clusters have been carried out, allowing a detailed analysis of the relative orientations of coordinated ligands. (Less)
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type
Contribution to journal
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published
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in
Dalton Transactions
issue
44
pages
6219 - 6230
publisher
Royal Society of Chemistry
external identifiers
  • wos:000260644000020
  • scopus:55349145282
ISSN
1477-9234
DOI
10.1039/b806846a
language
English
LU publication?
yes
id
501dcb48-296d-466f-838a-f6d2a13f6140 (old id 1283955)
date added to LUP
2009-02-09 11:04:35
date last changed
2017-10-22 03:57:00
@article{501dcb48-296d-466f-838a-f6d2a13f6140,
  abstract     = {The synthesis and reactivity of the thiophyne and furyne clusters [Ru-3(CO)(7)(mu-dppm)(mu(3)-eta(2)-C4H2E){mu-P(C4H3E)(2)}(mu-H)] (E = S, O) is reported. Addition of P(C4H3E)(3) to [Ru-3(CO)(10)(mu-dppm)] (1) at room temperature in the presence of Me3NO gives simple substitution products [Ru-3(CO)(9)(mu-dppm)-P(C4H3E)(3)}] (E = S, 2; E = O, 3). Mild thermolysis in the presence of further Me3NO affords the thiophyne and furyne complexes [Ru-3(CO)(7)(mu-dppm)(mu(3)-eta(2)-C4H2E){mu-P(C4H3E)(2)}(mu-H)] (E = S, 4; E = O, 6) resulting from both carbon-hydrogen and carbon-phosphorus bond activation. In each the C4H2E (E = S, O) ligand donates 4-electrons to the cluster and the rings are tilted with respect to the m-dppm and the phosphido-bridged open triruthenium unit. Heating 4 at 80 degrees C leads to the formation of the ring-opened cluster [Ru-3(CO)(5)(mu-CO)(mu-dppm)(mu(3)-eta(3)-SC4H3){mu-P(C4H3S)(2)}] (5) resulting from carbon-sulfur bond scission and carbon- hydrogen bond formation and containing a ring-opened mu(3)-eta(3)-1-thia-1,3-butadiene ligand. In contrast, a similar thermolysis of 3 affords the phosphinidene cluster [Ru-3(CO)(7)(mu-dppm)(mu(3)-eta(2)-C4H2O){mu(3)-P(C4H3O)}] (7) resulting from a second phosphorus-carbon bond cleavage and (presumably) elimination of furan. Treatment of 4 and 6 with PPh3 affords the simple phosphine-substituted products [Ru-3(CO)(6)(PPh3)(mu-ppm)(mu(3)-eta(2)-C4H2E){mu-P(C4H3E)(2)}(mu-H)] (E = S, 8; E = O, 9). Both thiophyne and furyne clusters 4 and 6 readily react with hydrogen bromide to give [Ru-3(CO)(6)Br(mu-Br)(mu-dppm)(mu(3)-eta(2)-eta(1)-C4H2E){mu-P(C4H3E)(2) }(mu-H)] (E = S, 10; E = O, 11) containing both terminal and bridging bromides. Here the alkynes bind in a highly unsymmetrical manner with one carbon acting as a bridging alkylidene and the second as a terminally bonded Fisher carbene. As far as we are aware, this binding mode has only previously been noted in ynamine complexes or those with metals in different oxidation states. The crystal structures of seven of these new triruthenium clusters have been carried out, allowing a detailed analysis of the relative orientations of coordinated ligands.},
  author       = {Uddin, Md. Nazim and Begum, Noorjahan and Hassan, Mohammad R. and Hogarth, Graeme and Kabir, Shariff E. and Miah, Md. Arzu and Nordlander, Ebbe and Tocher, Derek A.},
  issn         = {1477-9234},
  language     = {eng},
  number       = {44},
  pages        = {6219--6230},
  publisher    = {Royal Society of Chemistry},
  series       = {Dalton Transactions},
  title        = {Reactivity of triruthenium thiophyne and furyne clusters: competitive S-C and P-C bond cleavage reactions and the generation of highly unsymmetrical alkyne ligands},
  url          = {http://dx.doi.org/10.1039/b806846a},
  year         = {2008},
}