New ruthenium carbonyl clusters containing unusual mu(5)-sulfido-, mu(4)-benzyne-, and thianthrene-derived ligands: Insertion of ruthenium into the thianthrene ring by C-S activation
(2007) In Organometallics 26(18). p.4627-4633- Abstract
- Treatment of [Ru-3(CO)(12)] with thianthrene in refluxing toluene afforded [(mu(4)-S)Ru-4(mu-CO)(2)(CO)(9)(mu(4)-eta(2)-C6H4)] (1), [(mu(5)-S)Ru-6(mu-CO)(2)(CO)(15)(mu-eta(3)-C12H8S)] (2), and [(mu(5)-S)Ru-5(mu-CO)(2)(CO)(11)(mu-eta(3)-C12H8S)(mu(4)-eta(2)-C6H4)] (3) in 18%, 8%, and 16% yields, respectively. Thermolysis of 2 in refluxing heptane gave compounds 1 and 3. A similar thermolysis of 3 in refluxing toluene gave 1 in 90% yield. Treatment of 3 with neat MeCN afforded the labile compound [(mu(5)-S)Ru-5(mu-CO)(2)(CO)(10)(mu-eta(3)-C12H8S)(mu(4)-eta(2)-C6H4)(Me CN)] (4) in 73% yield. The reaction of 4 with P(OMe)(3) gave the substitution product [(mu(5)-S)Ru-5(mu-CO)(2)(CO)(10)(mu-eta(3)-C12H8S)(mu(4)-eta(2)-C6H4){P( OMe)(3)}] (5) in... (More)
- Treatment of [Ru-3(CO)(12)] with thianthrene in refluxing toluene afforded [(mu(4)-S)Ru-4(mu-CO)(2)(CO)(9)(mu(4)-eta(2)-C6H4)] (1), [(mu(5)-S)Ru-6(mu-CO)(2)(CO)(15)(mu-eta(3)-C12H8S)] (2), and [(mu(5)-S)Ru-5(mu-CO)(2)(CO)(11)(mu-eta(3)-C12H8S)(mu(4)-eta(2)-C6H4)] (3) in 18%, 8%, and 16% yields, respectively. Thermolysis of 2 in refluxing heptane gave compounds 1 and 3. A similar thermolysis of 3 in refluxing toluene gave 1 in 90% yield. Treatment of 3 with neat MeCN afforded the labile compound [(mu(5)-S)Ru-5(mu-CO)(2)(CO)(10)(mu-eta(3)-C12H8S)(mu(4)-eta(2)-C6H4)(Me CN)] (4) in 73% yield. The reaction of 4 with P(OMe)(3) gave the substitution product [(mu(5)-S)Ru-5(mu-CO)(2)(CO)(10)(mu-eta(3)-C12H8S)(mu(4)-eta(2)-C6H4){P( OMe)(3)}] (5) in 52% yield. Compounds 1-4 have been structurally characterized. Compound 1 contains a mu(4)-capping sulfido and a mu(4)-eta(2)-benzyne ligand, whereas 3, 4, and 5 contain mu(5)-sulfido and mu(4)-eta(2)-benzyne ligands. The latter three compounds provide rare examples of mu(5)-sulfido and metal-assisted opening of the thianthrene ligand on polynuclear centers. In compounds 1, 3, and 4 the mu(4)-eta(2)-benzyne ligand is perpendicular to the Ru-4 face of the clusters and represents a previously uncharacterized bonding mode for benzyne. (Less)
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https://lup.lub.lu.se/record/688767
- author
- Hassan, Mohammad R ; Kabir, Shariff E ; Nicholson, Brian K. ; Nordlander, Ebbe LU and Uddin, Nazim
- organization
- publishing date
- 2007
- type
- Contribution to journal
- publication status
- published
- subject
- in
- Organometallics
- volume
- 26
- issue
- 18
- pages
- 4627 - 4633
- publisher
- The American Chemical Society (ACS)
- external identifiers
-
- wos:000248865600038
- scopus:34548595385
- ISSN
- 1520-6041
- DOI
- 10.1021/om7004707
- language
- English
- LU publication?
- yes
- additional info
- The information about affiliations in this record was updated in December 2015. The record was previously connected to the following departments: Chemical Physics (S) (011001060)
- id
- 591fce28-f3c8-4e31-b135-c7b907342d1b (old id 688767)
- date added to LUP
- 2016-04-01 11:51:26
- date last changed
- 2022-01-26 19:14:51
@article{591fce28-f3c8-4e31-b135-c7b907342d1b,
abstract = {{Treatment of [Ru-3(CO)(12)] with thianthrene in refluxing toluene afforded [(mu(4)-S)Ru-4(mu-CO)(2)(CO)(9)(mu(4)-eta(2)-C6H4)] (1), [(mu(5)-S)Ru-6(mu-CO)(2)(CO)(15)(mu-eta(3)-C12H8S)] (2), and [(mu(5)-S)Ru-5(mu-CO)(2)(CO)(11)(mu-eta(3)-C12H8S)(mu(4)-eta(2)-C6H4)] (3) in 18%, 8%, and 16% yields, respectively. Thermolysis of 2 in refluxing heptane gave compounds 1 and 3. A similar thermolysis of 3 in refluxing toluene gave 1 in 90% yield. Treatment of 3 with neat MeCN afforded the labile compound [(mu(5)-S)Ru-5(mu-CO)(2)(CO)(10)(mu-eta(3)-C12H8S)(mu(4)-eta(2)-C6H4)(Me CN)] (4) in 73% yield. The reaction of 4 with P(OMe)(3) gave the substitution product [(mu(5)-S)Ru-5(mu-CO)(2)(CO)(10)(mu-eta(3)-C12H8S)(mu(4)-eta(2)-C6H4){P( OMe)(3)}] (5) in 52% yield. Compounds 1-4 have been structurally characterized. Compound 1 contains a mu(4)-capping sulfido and a mu(4)-eta(2)-benzyne ligand, whereas 3, 4, and 5 contain mu(5)-sulfido and mu(4)-eta(2)-benzyne ligands. The latter three compounds provide rare examples of mu(5)-sulfido and metal-assisted opening of the thianthrene ligand on polynuclear centers. In compounds 1, 3, and 4 the mu(4)-eta(2)-benzyne ligand is perpendicular to the Ru-4 face of the clusters and represents a previously uncharacterized bonding mode for benzyne.}},
author = {{Hassan, Mohammad R and Kabir, Shariff E and Nicholson, Brian K. and Nordlander, Ebbe and Uddin, Nazim}},
issn = {{1520-6041}},
language = {{eng}},
number = {{18}},
pages = {{4627--4633}},
publisher = {{The American Chemical Society (ACS)}},
series = {{Organometallics}},
title = {{New ruthenium carbonyl clusters containing unusual mu(5)-sulfido-, mu(4)-benzyne-, and thianthrene-derived ligands: Insertion of ruthenium into the thianthrene ring by C-S activation}},
url = {{http://dx.doi.org/10.1021/om7004707}},
doi = {{10.1021/om7004707}},
volume = {{26}},
year = {{2007}},
}