107052-99-3Relevant academic research and scientific papers
Intramolecular protonation and other mechanisms for substitution reactions of hydrido(thiolato)-and di(thiolato)-ruthenium(II) phosphine complexes
Jessop, Philip G.,James, Brian R.
, p. 75 - 86 (2008/10/08)
Reactions of cct-RuH(SR) (CO)2(PPh3)2 (1) (cct=cis, cis, trans) with R'SH provide cct-RuH(SR′)(CO)2(PPh3)2 (R = alkyl, aryl); based on described kinetic data, the proposed mechanism involves PPh3 loss, coordination of R′SH, intramolecular protonation of RS- by R′SH, and RSH elimination. The intramolecular protonation step circumvents a potentially slow RSH reductive elimination step. A similar mechanism is proposed for the thiol exchange reactions of cct-Ru(SR)2(CO)2(PPh3)2 (2). A corresponding dissociative mechanism is also proposed for the reaction of 1 with P(p-tolyl)3, which gives cct-RuH(SR)(CO)2(PPh3)(P(p-tolyl)3) and cct-RuH(SR)(CO)2-(P(p-tolyl)3)2. Other reactions described include the reactions of 1 with H2, CO, HCl and PPh3, and the reactions of 2 with P(p-tolyl)3 and H2. Exposure to light causes 2 to dimerize in solution.
Hydrido thiolato and thiolato complexes of ruthenium(II) carbonyl phosphines
Jessop, Philip G.,Rettig, Steven J.,Lee, Chung-Li,James, Brian R.
, p. 4617 - 4627 (2008/10/08)
Oxidative addition of RSH (R = H, alkyl, aryl) or RSSR (R = aryl) to Ru(CO)2L3 (L = PPh3, 1) yields respectively cct-RuH(SR)(CO)2L2 (type 2) (cct = cis,cis,trans) or cct-Ru(SR)2(CO)2L2 (type 3); a hydrido selenolate species is made similarly using PhSeH. Methods for in situ formation of corresponding mixed bis(thiolate) species are also given. 1 is generally unreactive toward thioethers, although with propylene sulfide cct-Ru(η2-S2) (CO)2L2 is produced. Metathesis reactions of cct-RuCl2(CO)2L2 with NaSR salts yield 3 (R = aryl) or, when R = Et, cct-RuCl(SEt)(CO)2L2 or [L(CO)2Ru(μ2 -SEt)2(μ3-SEt)Na(THF)]2 (4), depending on reaction conditions. The complexes are characterized by IR spectroscopy, 1H, 31P, and, in some cases, 13C NMR spectroscopy, and for 2g and 3g (R = SC6H4pMe) and 4, X-ray crystallography. All three complexes crystallized in the space group P1. For 2g, a = 12.340 (4) A?, b = 14.948 (3) A?, c = 10.684 (4) A?, α = 90.05 (3)°, β = 99.27 (3)°, γ = 86.84 (3)°, V = 1942 (1) A?3, and Z = 2; the structure refined to R = 0.032 and Rw = 0.037 for 7174 reflections with Fo2 > 3σ(Fo2). Corresponding crystallographic data for 3g are a = 13.173 (3) A?, b = 19.766 (4) A?, c = 9.770 (4) A?, α = 98.26 (2)°, β = 91.24 (3)°, γ = 78.31 (2)°, V = 2465 (1) A?3, Z = 2, R = 0.041, and Rw = 0.043 for 3597 reflections; for 4, a = 12.189 (3) A?, b = 13.124 (3) A?, c = 12.032 (4) A?, α = 99.70 (2)°, β = 110.61 (2)°, γ = 67.95 (2)°, V = 1668.4 (8) A?3, Z = 1, R = 0.039, and Rw = 0.043 for 4252 reflections. 4 has an unprecedented network of transition-metal and alkali-metal ions bridged by thiolate ligands: four thiolates bridge one Ru and one Na, and two thiolates bridge one Ru and two Na atoms. The geometries at Ru and Na are close to octahedral and square pyramidal, respectively. Trends are noted for the 1H NMR shifts and 2JPH values for the hydride in 2, and an additivity rule formulated for the 31P shift within the cct-Ru(SR)(SR′)(CO)2(PPh3)2 species. Limited kinetic data suggest that the oxidative addition reactions to 1 probably proceed via a nonradical process, following dissociation of a PPh3 ligand.
