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Reactivity of the unsaturated triosmium cluster Os-3(CO)(8)(mu(3)-eta(2)-Ph2PCH2P(Ph)C6H4)(mu-H) with benzothiophene: Activation of a P-C bond in diphosphine and a C-H bond in benzothiophene

Kabir, SE; Miah, MA; Sarker, NC; Hussain, GMG; Hardcastle, KI; Nordlander, Ebbe LU and Rosenberg, E (2005) In Organometallics 24(13). p.3315-3320
Abstract
Treatment of the electronically unsaturated cluster Os-3(CO)(8)(mu(3)-eta(2)-Ph2PCH2P(Ph)C6H4)(mu-H) (1) with benzothiophene in refluxing m-xylene afforded Os-3(CO)(7)(mu-PPh2)(mu-PMePh)(mu(3)-eta(2)-C6H4) (2), Os-3(CO)(7)(mu(3)-eta(2)-PPh(C6H4)CH2PPh)(mu(3)-eta(3)-SC8H5)(mu-H) (3), and Os-3(CO)(8)(mu-CO)(mu(3)-eta(2)-PPh(C6H4)CH2PPh) (4). Thermolysis of 1 in refluxing toluene for 35 h afforded only 4, whereas in refluxing m-xylene it gave both 4 and 2. Compound 4 can also be obtained from the thermolysis of Os-3(CO)(9)(mu(3)-eta(2)-PPh(C6H4)CH2PPh2)(mu-H) (5) in refluxing toluene. All the complexes have been structurally characterized. Compound 3 contains a unique example of a mu(3)-eta(2) benzothienyl ligand coordinated through the... (More)
Treatment of the electronically unsaturated cluster Os-3(CO)(8)(mu(3)-eta(2)-Ph2PCH2P(Ph)C6H4)(mu-H) (1) with benzothiophene in refluxing m-xylene afforded Os-3(CO)(7)(mu-PPh2)(mu-PMePh)(mu(3)-eta(2)-C6H4) (2), Os-3(CO)(7)(mu(3)-eta(2)-PPh(C6H4)CH2PPh)(mu(3)-eta(3)-SC8H5)(mu-H) (3), and Os-3(CO)(8)(mu-CO)(mu(3)-eta(2)-PPh(C6H4)CH2PPh) (4). Thermolysis of 1 in refluxing toluene for 35 h afforded only 4, whereas in refluxing m-xylene it gave both 4 and 2. Compound 4 can also be obtained from the thermolysis of Os-3(CO)(9)(mu(3)-eta(2)-PPh(C6H4)CH2PPh2)(mu-H) (5) in refluxing toluene. All the complexes have been structurally characterized. Compound 3 contains a unique example of a mu(3)-eta(2) benzothienyl ligand coordinated through the sulfur atom and the C-C double bond of the five-membered ring in a sigma,pi vinyl fashion. This coordination mode results in the rupture of one osmium-osmium bond, whereas the basic triangular metal framework is retained in the case of 2 and 4, which are derived from the activation of P-C and C-H bonds of 1 and do not contain any benzothiophene-derived ligand. (Less)
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author
organization
publishing date
type
Contribution to journal
publication status
published
subject
in
Organometallics
volume
24
issue
13
pages
3315 - 3320
publisher
The American Chemical Society
external identifiers
  • wos:000229878200036
  • scopus:23144446370
ISSN
1520-6041
DOI
10.1021/om050110k
language
English
LU publication?
yes
id
0adcabc4-42a0-4736-9360-a2d5c3c993b6 (old id 235524)
date added to LUP
2007-08-23 16:23:37
date last changed
2017-01-01 04:19:40
@article{0adcabc4-42a0-4736-9360-a2d5c3c993b6,
  abstract     = {Treatment of the electronically unsaturated cluster Os-3(CO)(8)(mu(3)-eta(2)-Ph2PCH2P(Ph)C6H4)(mu-H) (1) with benzothiophene in refluxing m-xylene afforded Os-3(CO)(7)(mu-PPh2)(mu-PMePh)(mu(3)-eta(2)-C6H4) (2), Os-3(CO)(7)(mu(3)-eta(2)-PPh(C6H4)CH2PPh)(mu(3)-eta(3)-SC8H5)(mu-H) (3), and Os-3(CO)(8)(mu-CO)(mu(3)-eta(2)-PPh(C6H4)CH2PPh) (4). Thermolysis of 1 in refluxing toluene for 35 h afforded only 4, whereas in refluxing m-xylene it gave both 4 and 2. Compound 4 can also be obtained from the thermolysis of Os-3(CO)(9)(mu(3)-eta(2)-PPh(C6H4)CH2PPh2)(mu-H) (5) in refluxing toluene. All the complexes have been structurally characterized. Compound 3 contains a unique example of a mu(3)-eta(2) benzothienyl ligand coordinated through the sulfur atom and the C-C double bond of the five-membered ring in a sigma,pi vinyl fashion. This coordination mode results in the rupture of one osmium-osmium bond, whereas the basic triangular metal framework is retained in the case of 2 and 4, which are derived from the activation of P-C and C-H bonds of 1 and do not contain any benzothiophene-derived ligand.},
  author       = {Kabir, SE and Miah, MA and Sarker, NC and Hussain, GMG and Hardcastle, KI and Nordlander, Ebbe and Rosenberg, E},
  issn         = {1520-6041},
  language     = {eng},
  number       = {13},
  pages        = {3315--3320},
  publisher    = {The American Chemical Society},
  series       = {Organometallics},
  title        = {Reactivity of the unsaturated triosmium cluster Os-3(CO)(8)(mu(3)-eta(2)-Ph2PCH2P(Ph)C6H4)(mu-H) with benzothiophene: Activation of a P-C bond in diphosphine and a C-H bond in benzothiophene},
  url          = {http://dx.doi.org/10.1021/om050110k},
  volume       = {24},
  year         = {2005},
}