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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, S; Rana, S; Tocher, DA; Hogarth, G; Nordlander, E; Kabir, SE; (2009) 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. J ORGANOMET CHEM , 694 (20) 3312 - 3319. 10.1016/j.jorganchem.2009.06.005.

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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),kappa(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),kappa(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.

Type:Article
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
DOI:10.1016/j.jorganchem.2009.06.005
Keywords:Diphosphines, Triruthenium, Carbonyl, Tri(2-thienyl) phosphine, Tri(2-furyl) phosphine, X-ray structures, ETHYLENE TRIMERIZATION CATALYSTS, 4-MEMBERED CHELATE RINGS, X-RAY STRUCTURES, ASYMMETRIC HYDROGENATION, DIPHOSPHINOAMINE LIGANDS, MOLECULAR-STRUCTURES, COORDINATION MODES, STERIC ACTIVATION, RHODIUM CATALYST, P-C
UCL classification:UCL > School of BEAMS > Faculty of Maths and Physical Sciences > Chemistry

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