Reactivity of the triruthenium ortho-metalated cluster [Ru3(CO)9{μ3-η1,κ1,κ2-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

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)

“…However, these particular ligands are known to undergo activation by carbon-phosphorus bond cleavage, leading to phosphido and furyl/thienyl moieties. Recently, we and others have shown that tris(2-thienyl)phosphine (PTh 3 ) undergoes carbon-phosphorus and carbonhydrogen bond activation in reactions with polynuclear ruthenium, 34,35,36,37 iron, 38 and osmium carbonyls, 23 revealing a wide diversity of coordination modes of these ligands upon activation.…”

“…38 M 3 (CO) 12 Twenty years ago, Vahrenkamp and co-workers reported the low-yield preparation of the triand mononuclear complexes Ru 3 (CO) 10 (PTh 3 ) 2 and trans-Ru(CO) 3 (PTh 3 ) 2 , from the reaction of Ru 3 (CO) 12 with PTh 3 . 17 As a part of our ongoing research on the reactivity of functionalized phosphines with transition metal carbonyls, 21,22,23,24,25,26,29,34,35,36,37,38 we have now re-examined the M A N U S C R I P T A C C E P T E D ACCEPTED MANUSCRIPT 4 reaction of PTh 3 with Ru 3 (CO) 12 and report the isolation of simple trinuclear substitution products, along with tri-, tetra-and pentanuclear clusters containing ancillary ligands derived from a series of carbon-hydrogen, carbon-phosphorus, and carbon-sulfur bond scission events involving the PTh 3 ligand(s). 12 with PTh 3 …”