297180-61-1Relevant articles and documents
Chelation kinetics of bidentate phosphine ligands on pentacoordinate ruthenium carbonyl complexes
Bunten, Kevin A.,Farrar, David H.,Po?, Anthony J.,Lough, Alan J.
, p. 3674 - 3682 (2008/10/08)
Chelation kinetics of the complexes Ru(CO)4(η1-(P-P)) have been studied in heptane, where P-P = Ph2P(CH2)nPPh2 (n = 1, 2, 3, or 4, i.e., dppm, dppe, dppp, or dppb), Ph2P(NMe)PPh2 (dppma), Ph2P(o-C6H4)PPh2 (dpp-benzene), or R2P(CH2)2PR2 (R = Me or Cy, i.e., dmpe or dcpe). The complexes were prepared in situ by reaction of the bidentate ligands with Ru(CO)4(C2H4), which itself was prepared in situ by photolysis of Ru3(CO)12 under C2H4. The initially formed Ru(CO)4(η1-(P-P)) complexes react cleanly to form axial-equatorial Ru(CO)3(η2-(P-P)), as shown by the crystallographic structures of the products when P-P = dppe, dmpe, and dpp-benzene and the close similarity of their FTIR spectra to those of the other products. The chelated products undergo further reaction in solution or the solid state, and the product when P-P = dppma has been characterized by crystallography as Ru2-(CO)3(μ-PPh2)(μ-Ph2PNMePPh2). The kinetics of the displacement of CO from Ru(CO)4(η1-(P-P)) in n-heptane are characterized by ΔH? values that are lower by up to 9 kcal mol-1 than those of their monodentate P-donor analogues. ΔS? values range from quite positive to slightly negative and suggest a trend from purely dissociative to appreciably associative mechanisms along the series P-P = dpp-benzene 4L complexes when L = monodentate P-donor ligands.
Reactive mono- and dinuclear bis(diphenylphosphino)methane derivatives of ruthenium carbonyls: Ru(CO)4(η1-dppm) and Ru2(CO)7(μ-dppm)
Kiel, Gong-Yu,Takats, Josef
, p. 839 - 840 (2008/10/08)
Reaction of bis(diphenylphosphino)methane with in situ generated Ru(CO)4(η2-CH2CHCH3) gives Ru-(CO)4(η1-dppm) (1). Photolysis of 1 and Ru(CO)5 or that of Ru3(CO)10(μ-dppm) in the presence of CO yields Ru2-(CO)7(μ-dppm) (2). Evidence for high reactivity of these complexes is presented by the reaction of 2 with CH2N2 and HCCH and that of 1 with [Rh(CO)2(solv)2]+ and [Rh-(CO)2Cl]2, all occurring below 0°C.
