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Thermal transformations of tris(2-thienyl)phosphine (PTh3) at low-valent ruthenium cluster centers : Part I. Carbon-hydrogen, carbon-phosphorus and carbon-sulfur bond activation yielding Ru3(CO)8L{μ-Th2P(C4H2S)}(μ-H) (L = CO, PTh3), Ru3(CO)7(μ-PTh2)232-C4H2S), Ru4(CO)9(μ-CO)242-C4H2S)(μ4-PTh) and Ru5(CO)11(μ-PTh2)(μ44-C4H3)(μ4-S)

Uddin, Md Miaz; Begum, Noorjahan; Ghosh, Shishir; Sarker, Jagodish C.; Tocher, Derek A; Hogarth, Graeme; Richmond, Michael G.; Nordlander, Ebbe LU and Kabir, Shariff E (2016) In Journal of Organometallic Chemistry 812. p.197-206
Abstract

Reaction of Ru3(CO)12 with tris(2-thienyl)phosphine (PTh3) in CH2Cl2 at room temperature or in THF in the presence of a catalytic amount of Na[Ph2CO] furnishes the carbonyl substitution products Ru3(CO)11(PTh3) (1), Ru3(CO)10(PTh3)2 (2), and Ru3(CO)9(PTh3)3 (3). Heating 1 in toluene affords the cyclometalated cluster Ru3(CO)9{μ-Th2P(C4H2S)}(μ-H) (4) resulting from carbonyl loss and carbon-hydrogen bond activation, and both 4 and the substituted derivative... (More)

Reaction of Ru3(CO)12 with tris(2-thienyl)phosphine (PTh3) in CH2Cl2 at room temperature or in THF in the presence of a catalytic amount of Na[Ph2CO] furnishes the carbonyl substitution products Ru3(CO)11(PTh3) (1), Ru3(CO)10(PTh3)2 (2), and Ru3(CO)9(PTh3)3 (3). Heating 1 in toluene affords the cyclometalated cluster Ru3(CO)9{μ-Th2P(C4H2S)}(μ-H) (4) resulting from carbonyl loss and carbon-hydrogen bond activation, and both 4 and the substituted derivative Ru3(CO)8{μ-Th2P(C4H2S)}(PTh3)(μ-H) (5) resulted from the direct reaction of Ru3(CO)12 and PTh3 at 110 °C in toluene. Interestingly, thermolysis of 2 in benzene at 80 °C affords 5 together with phosphido-bridged Ru3(CO)7(μ-PTh2)232-C4H2S) (6) resulting from both phosphorus-carbon and carbon-hydrogen bond activation of coordinated PTh3 ligand(s). Cluster 6 is the only product of the thermolysis of 2 in toluene. Heating cyclometalated 4 with Ru3(CO)12 in toluene at 110 °C yielded the tetranuclear phosphinidine cluster, Ru4(CO)9(μ-CO)242-C4H2S)(μ4-PTh) (7), resulting from carbon-phosphorus bond scission, together with the pentaruthenium sulfide cluster, Ru5(CO)11(μ-PTh2)(μ44-C4H3)(μ4-S) (8), in which sulfur is extruded from a thiophene ring. All the new compounds were characterized by elemental analysis, mass spectrometry, IR and NMR spectroscopy, and by single crystal X-ray diffraction analysis in case of clusters 4, 6, 7, and 8. Cluster 4 consists of a triangular ruthenium framework containing a μ3-Th2P(C4H2S) ligand, while 6 consists of a ruthenium triangle containing η23-thiophyne ligand and two edge-bridging PTh2 ligands. Cluster 7 exhibits a distorted square arrangement of ruthenium atoms that are capped on one side by a μ4-phosphinidene ligand and on the other by a 4e donating μ42-C4H2S ligand. The structure of 8 represents a rare example of a pentaruthenium wing-tip bridged-butterfly skeleton capped by μ4-S and μ44-C4H3 ligands. The compounds 4, 6, 7, and 8 have been examined by density functional theory (DFT), and the lowest energy structure computed coincides with the X-ray diffraction structure. The hemilabile nature of the activated thienyl ligand in 4 and 6 has also been computationally investigated.

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Contribution to journal
publication status
published
subject
keywords
C-P, C-H, and C-S bond scission, DFT, Functionalized phosphine, Ruthenium cluster, Thienyl, X-ray diffraction
in
Journal of Organometallic Chemistry
volume
812
pages
10 pages
publisher
Elsevier
external identifiers
  • scopus:84937896981
  • wos:000378192200024
ISSN
0022-328X
DOI
10.1016/j.jorganchem.2015.06.026
language
English
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yes
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a66b595a-6ec3-44bc-91de-2daa7355ff36
date added to LUP
2017-02-01 09:37:20
date last changed
2017-09-18 11:35:00
@article{a66b595a-6ec3-44bc-91de-2daa7355ff36,
  abstract     = {<p>Reaction of Ru<sub>3</sub>(CO)<sub>12</sub> with tris(2-thienyl)phosphine (PTh<sub>3</sub>) in CH<sub>2</sub>Cl<sub>2</sub> at room temperature or in THF in the presence of a catalytic amount of Na[Ph<sub>2</sub>CO] furnishes the carbonyl substitution products Ru<sub>3</sub>(CO)<sub>11</sub>(PTh<sub>3</sub>) (1), Ru<sub>3</sub>(CO)<sub>10</sub>(PTh<sub>3</sub>)<sub>2</sub> (2), and Ru<sub>3</sub>(CO)<sub>9</sub>(PTh<sub>3</sub>)<sub>3</sub> (3). Heating 1 in toluene affords the cyclometalated cluster Ru<sub>3</sub>(CO)<sub>9</sub>{μ-Th<sub>2</sub>P(C<sub>4</sub>H<sub>2</sub>S)}(μ-H) (4) resulting from carbonyl loss and carbon-hydrogen bond activation, and both 4 and the substituted derivative Ru<sub>3</sub>(CO)<sub>8</sub>{μ-Th<sub>2</sub>P(C<sub>4</sub>H<sub>2</sub>S)}(PTh<sub>3</sub>)(μ-H) (5) resulted from the direct reaction of Ru<sub>3</sub>(CO)<sub>12</sub> and PTh<sub>3</sub> at 110 °C in toluene. Interestingly, thermolysis of 2 in benzene at 80 °C affords 5 together with phosphido-bridged Ru<sub>3</sub>(CO)<sub>7</sub>(μ-PTh<sub>2</sub>)<sub>2</sub>(μ<sub>3</sub>-η<sup>2</sup>-C<sub>4</sub>H<sub>2</sub>S) (6) resulting from both phosphorus-carbon and carbon-hydrogen bond activation of coordinated PTh<sub>3</sub> ligand(s). Cluster 6 is the only product of the thermolysis of 2 in toluene. Heating cyclometalated 4 with Ru<sub>3</sub>(CO)<sub>12</sub> in toluene at 110 °C yielded the tetranuclear phosphinidine cluster, Ru<sub>4</sub>(CO)<sub>9</sub>(μ-CO)<sub>2</sub>(μ<sub>4</sub>-η<sup>2</sup>-C<sub>4</sub>H<sub>2</sub>S)(μ<sub>4</sub>-PTh) (7), resulting from carbon-phosphorus bond scission, together with the pentaruthenium sulfide cluster, Ru<sub>5</sub>(CO)<sub>11</sub>(μ-PTh<sub>2</sub>)(μ<sub>4</sub>-η<sup>4</sup>-C<sub>4</sub>H<sub>3</sub>)(μ<sub>4</sub>-S) (8), in which sulfur is extruded from a thiophene ring. All the new compounds were characterized by elemental analysis, mass spectrometry, IR and NMR spectroscopy, and by single crystal X-ray diffraction analysis in case of clusters 4, 6, 7, and 8. Cluster 4 consists of a triangular ruthenium framework containing a μ<sub>3</sub>-Th<sub>2</sub>P(C<sub>4</sub>H<sub>2</sub>S) ligand, while 6 consists of a ruthenium triangle containing η<sup>2</sup>-μ<sub>3</sub>-thiophyne ligand and two edge-bridging PTh<sub>2</sub> ligands. Cluster 7 exhibits a distorted square arrangement of ruthenium atoms that are capped on one side by a μ<sub>4</sub>-phosphinidene ligand and on the other by a 4e donating μ<sub>4</sub>-η<sup>2</sup>-C<sub>4</sub>H<sub>2</sub>S ligand. The structure of 8 represents a rare example of a pentaruthenium wing-tip bridged-butterfly skeleton capped by μ<sub>4</sub>-S and μ<sub>4</sub>-η<sup>4</sup>-C<sub>4</sub>H<sub>3</sub> ligands. The compounds 4, 6, 7, and 8 have been examined by density functional theory (DFT), and the lowest energy structure computed coincides with the X-ray diffraction structure. The hemilabile nature of the activated thienyl ligand in 4 and 6 has also been computationally investigated.</p>},
  author       = {Uddin, Md Miaz and Begum, Noorjahan and Ghosh, Shishir and Sarker, Jagodish C. and Tocher, Derek A and Hogarth, Graeme and Richmond, Michael G. and Nordlander, Ebbe and Kabir, Shariff E},
  issn         = {0022-328X},
  keyword      = {C-P, C-H, and C-S bond scission,DFT,Functionalized phosphine,Ruthenium cluster,Thienyl,X-ray diffraction},
  language     = {eng},
  month        = {06},
  pages        = {197--206},
  publisher    = {Elsevier},
  series       = {Journal of Organometallic Chemistry},
  title        = {Thermal transformations of tris(2-thienyl)phosphine (PTh<sub>3</sub>) at low-valent ruthenium cluster centers : Part I. Carbon-hydrogen, carbon-phosphorus and carbon-sulfur bond activation yielding Ru<sub>3</sub>(CO)<sub>8</sub>L{μ-Th<sub>2</sub>P(C<sub>4</sub>H<sub>2</sub>S)}(μ-H) (L = CO, PTh<sub>3</sub>), Ru<sub>3</sub>(CO)<sub>7</sub>(μ-PTh<sub>2</sub>)<sub>2</sub>(μ<sub>3</sub>-η<sup>2</sup>-C<sub>4</sub>H<sub>2</sub>S), Ru<sub>4</sub>(CO)<sub>9</sub>(μ-CO)<sub>2</sub>(μ<sub>4</sub>-η<sup>2</sup>-C<sub>4</sub>H<sub>2</sub>S)(μ<sub>4</sub>-PTh) and Ru<sub>5</sub>(CO)<sub>11</sub>(μ-PTh<sub>2</sub>)(μ<sub>4</sub>-η<sup>4</sup>-C<sub>4</sub>H<sub>3</sub>)(μ<sub>4</sub>-S)},
  url          = {http://dx.doi.org/10.1016/j.jorganchem.2015.06.026},
  volume       = {812},
  year         = {2016},
}