60879-59-6Relevant academic research and scientific papers
Formation of ammonia in the reactions of a tungsten dinitrogen with ruthenium dihydrogen complexes under mild reaction conditions
Nishibayashi,Takemoto,Iwai,Hidai
, p. 5946 - 5957 (2008/10/08)
Treatment of cis-[W(N2)2(PMe2Ph)4] (5) with an equilibrium mixture of trans-[RuCl(η2-H2)(dppp)2]X (3) with pKa = 4.4 and [RuCl(dppp)2]X (4) [X = PF6, BF4, or OTf; dppp = 1,3-bis(diphenylphosphino)propane] containing 10 equiv of the Ru atom based on tungsten in benzene-dichloroethane at 55°C for 24 h under 1 atm of H2 gave NH3 in 45-55% total yields based on tungsten, together with the formation of trans-[RuHCl(dppp)2] (6). Free NH3 in 9-16% yields was observed in the reaction mixture, and further NH3 in 36-45% yields was released after base distillation. Detailed studies on the reaction of 5 with numerous Ru(η2-H2) complexes showed that the yield of NH3 produced critically depended upon the pKa value of the employed Ru(η2-H2) complexes. When 5 was treated with 10 equiv of trans-[RuCl(η2-H2)(dppe)2]X (8) with pKa = 6.0 [X = PF6, BF4, or OTf; dppe = 1,2-bis(diphenylphosphino)ethane] under 1 atm of H2, NH3 was formed in higher yields (up to 79% total yield) compared with the reaction with an equilibrium mixture of 3 and 4. If the pKa value of a Ru(η2-H2) complex was increased up to about 10, the yield of NH3 was remarkably decreased. In these reactions, heterolyfic cleavage of H2 seems to occur at the Ru center via nucleophilic attack of the coordinated N2 on the coordinated H2 where a proton (H+) is used for the protonation of the coordinated N2 and a hydride (H-) remains at the Ru atom. Treatment of 5, trans-[W(N2)2(PMePh2)4] (14), or trans-[M(N2)2(dppe)2] [M = Mo (1), W (2)] with Ru(η2-H2)complexes at room temperature led to isolation of intermediate hydrazido(2-) complexes such as trans-[W(OTf)(NNH2)(PMe2Ph)4]OTf (19), trans-[W(OTf)(NNH2)(PMePh2)4]OTf (20), and trans-[WX(NNH2)(dppe)2]+ [X = O[Tf (15), F (16)]. The molecular structure of 19 was determined by X-ray analysis. Further ruthenium-assisted protonation of . hydrazido(2-) intermediates such as 19 with H2 at 55 °C was considered to result in the formation of NH3, concurrent with the generation of W(VI)species. All of the electrons required for the reduction of N2 are provided by the zerovalent tungsten.
OCTAHEDRAL AND TRIGONAL-BIPYRAMIDAL COMPLEXES OF RUTHENIUM(II) WITH BIDENTATE PHOSPHINE LIGANDS
Briggs, Josie C.,McAuliffe, Charles A.,Dyer, Geoffrey
, p. 423 - 428 (2007/10/02)
Six- and five-co-ordinate complexes of ruthenium(II) with the unsymmetrical diphosphine ligand Ph2P(CH2)3PMe2 have been prepared.Phosphorus-31 n.m.r. spectroscopy indicates that octahedral complexes , , and ClO4 (P-P = diphosphine ligand) have the all-trans arrangement with Me2P trans to Me2P and Ph2P trans to Ph2P.The five-co-ordinate complexes BPh4, where X = Cl or H, are not fluxional at room temperature and have a trigonal-bipyramidal structure with axial PMe2 groups and equatorial PPh2 groups.Similar structures are proposed for analogous complexes of Ph2P(CH2)3PMePh and of Ph2P(CH2)3PPh2.
