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)2(μ3-η2-C4H2S), Ru4(CO)9(μ-CO)2(μ4-η2-C4H2S)(μ4-PTh) and Ru5(CO)11(μ-PTh2)(μ4-η4-C4H3)(μ4-S)
(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)2(μ3-η2-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)2(μ4-η2-C4H2S)(μ4-PTh) (7), resulting from carbon-phosphorus bond scission, together with the pentaruthenium sulfide cluster, Ru5(CO)11(μ-PTh2)(μ4-η4-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 η2-μ3-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 μ4-η2-C4H2S ligand. The structure of 8 represents a rare example of a pentaruthenium wing-tip bridged-butterfly skeleton capped by μ4-S and μ4-η4-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.
(Less)
- author
- 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
- organization
- publishing date
- 2016-06-15
- type
- 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
- LU publication?
- yes
- id
- a66b595a-6ec3-44bc-91de-2daa7355ff36
- date added to LUP
- 2017-02-01 09:37:20
- date last changed
- 2024-06-16 01:48:02
@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}},
keywords = {{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}},
doi = {{10.1016/j.jorganchem.2015.06.026}},
volume = {{812}},
year = {{2016}},
}