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Reactivity of the triruthenium ortho-metalated cluster [Ru-3(CO)(9){mu(3)- eta(1), kappa(1),kappa(2)-PhP( C6H4) CH2PPh}] with tri(2-thienyl) phosphine and tri( 2-furyl) phosphine: Formation of 1,3-diphenyl-2,3-dihydro-1H-1,3-benzodiphosphine complexes via phosphorus-carbon bond formation

Ghosh, Shishir; Rana, Shahed; Tocher, Derek A.; Hogarth, Graeme; Nordlander, Ebbe LU and Kabir, Shariff E. (2009) In Journal of Organometallic Chemistry 694(20). p.3312-3319
Abstract
Reaction of [Ru(CO)(9){mu(3-)eta(1),kappa(1),kappa(2)-PhP(C6H4)CH2PPh}] (1) with tri(2-thienyl) phosphine (PTh3) in refluxing THF afforded [Ru-3(CO)(9)(PTh3)(mu-dpbm)] (3){dpbm = PhP(C6H4)(CH2)PPh} and [Ru-3(CO)(6)(mu-CO)(2){mu-kappa(1),eta(1)-PTh2(C4H2S)}{mu(3)-kappa(1),ka ppa(2)-Ph2PCH2PPh}] (5) in 18% and 12% yields, respectively, while a similar reaction with tri(2-furyl)phosphine (PFu(3)) gave [Ru-3(CO)(9)(PFu(3))(mu-dpbm)] (4) and [Ru-3(CO)(7)(mu-eta(1),eta(2)-C4H3O)(mu-PFu(2)){mu(3)-eta(1),kappa(1),ka ppa(2)-PhP(C6H4)CH2PPh}] (6) in 24% and 27% yields, respectively. Compounds 2 and 4 are phosphine adducts of 1 in which the diphosphine ligand is transformed into 1,3-diphenyl-2,3-dihydro-1H-1,3-benzodiphosphine(dpbm) via... (More)
Reaction of [Ru(CO)(9){mu(3-)eta(1),kappa(1),kappa(2)-PhP(C6H4)CH2PPh}] (1) with tri(2-thienyl) phosphine (PTh3) in refluxing THF afforded [Ru-3(CO)(9)(PTh3)(mu-dpbm)] (3){dpbm = PhP(C6H4)(CH2)PPh} and [Ru-3(CO)(6)(mu-CO)(2){mu-kappa(1),eta(1)-PTh2(C4H2S)}{mu(3)-kappa(1),ka ppa(2)-Ph2PCH2PPh}] (5) in 18% and 12% yields, respectively, while a similar reaction with tri(2-furyl)phosphine (PFu(3)) gave [Ru-3(CO)(9)(PFu(3))(mu-dpbm)] (4) and [Ru-3(CO)(7)(mu-eta(1),eta(2)-C4H3O)(mu-PFu(2)){mu(3)-eta(1),kappa(1),ka ppa(2)-PhP(C6H4)CH2PPh}] (6) in 24% and 27% yields, respectively. Compounds 2 and 4 are phosphine adducts of 1 in which the diphosphine ligand is transformed into 1,3-diphenyl-2,3-dihydro-1H-1,3-benzodiphosphine(dpbm) via phosphorus-carbon bond formation. Cluster 5 results from metalation of a thienyl ring, the cleved proton being transfoerred to the diphosphine.Carbon-phosphorus bond clevarge of a PFu(3) ligand is observed in 6 to afford a phosphido-bridge and furyl fragment, the latter bridging in a sigma,pi-vinyl fashion. The molecular strucutres of 3,5 and 6 have been determined by X-ray diffraction studies. (C) 2009 Published by Elsevier B.V. (Less)
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Contribution to journal
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published
subject
keywords
X-ray structures, Tri(2-furyl) phosphine, Tri(2-thienyl) phosphine, Carbonyl, Diphosphines, Triruthenium
in
Journal of Organometallic Chemistry
volume
694
issue
20
pages
3312 - 3319
publisher
Elsevier
external identifiers
  • wos:000268988500014
  • scopus:68549120870
ISSN
0022-328X
DOI
10.1016/j.jorganchem.2009.06.005
language
English
LU publication?
yes
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a7a78811-e473-454f-9068-799d1603b868 (old id 1477242)
date added to LUP
2009-09-23 13:07:00
date last changed
2017-01-01 06:09:24
@article{a7a78811-e473-454f-9068-799d1603b868,
  abstract     = {Reaction of [Ru(CO)(9){mu(3-)eta(1),kappa(1),kappa(2)-PhP(C6H4)CH2PPh}] (1) with tri(2-thienyl) phosphine (PTh3) in refluxing THF afforded [Ru-3(CO)(9)(PTh3)(mu-dpbm)] (3){dpbm = PhP(C6H4)(CH2)PPh} and [Ru-3(CO)(6)(mu-CO)(2){mu-kappa(1),eta(1)-PTh2(C4H2S)}{mu(3)-kappa(1),ka ppa(2)-Ph2PCH2PPh}] (5) in 18% and 12% yields, respectively, while a similar reaction with tri(2-furyl)phosphine (PFu(3)) gave [Ru-3(CO)(9)(PFu(3))(mu-dpbm)] (4) and [Ru-3(CO)(7)(mu-eta(1),eta(2)-C4H3O)(mu-PFu(2)){mu(3)-eta(1),kappa(1),ka ppa(2)-PhP(C6H4)CH2PPh}] (6) in 24% and 27% yields, respectively. Compounds 2 and 4 are phosphine adducts of 1 in which the diphosphine ligand is transformed into 1,3-diphenyl-2,3-dihydro-1H-1,3-benzodiphosphine(dpbm) via phosphorus-carbon bond formation. Cluster 5 results from metalation of a thienyl ring, the cleved proton being transfoerred to the diphosphine.Carbon-phosphorus bond clevarge of a PFu(3) ligand is observed in 6 to afford a phosphido-bridge and furyl fragment, the latter bridging in a sigma,pi-vinyl fashion. The molecular strucutres of 3,5 and 6 have been determined by X-ray diffraction studies. (C) 2009 Published by Elsevier B.V.},
  author       = {Ghosh, Shishir and Rana, Shahed and Tocher, Derek A. and Hogarth, Graeme and Nordlander, Ebbe and Kabir, Shariff E.},
  issn         = {0022-328X},
  keyword      = {X-ray structures,Tri(2-furyl) phosphine,Tri(2-thienyl) phosphine,Carbonyl,Diphosphines,Triruthenium},
  language     = {eng},
  number       = {20},
  pages        = {3312--3319},
  publisher    = {Elsevier},
  series       = {Journal of Organometallic Chemistry},
  title        = {Reactivity of the triruthenium ortho-metalated cluster [Ru-3(CO)(9){mu(3)- eta(1), kappa(1),kappa(2)-PhP( C6H4) CH2PPh}] with tri(2-thienyl) phosphine and tri( 2-furyl) phosphine: Formation of 1,3-diphenyl-2,3-dihydro-1H-1,3-benzodiphosphine complexes via phosphorus-carbon bond formation},
  url          = {http://dx.doi.org/10.1016/j.jorganchem.2009.06.005},
  volume       = {694},
  year         = {2009},
}