Welcome to LookChem.com Sign In|Join Free

Article Doi

Synthesis, Crystal Structures and Reactivity of Ruthenium-(II) and -(III) Complexes containing β-Ketophosphine or Phosphino Enolate Ligands

DOI: 10.1039/DT9950000851

Source and publish data:

Journal of the Chemical Society, Dalton Transactions p. 851 - 862 (1995)

Update date:2022-08-04

Topics:

Authors:

Braunstein, PierreBraunstein, Pierre

Chauvin, YvesChauvin, Yves

Naehring, JensNaehring, Jens

Dusausoy, YvesDusausoy, Yves

Bayeul, DanielBayeul, Daniel

et al.et al.

Read Full Text PDF DownLoad Join now for total 90,000,000 free articles

Article abstract of DOI:10.1039/DT9950000851

Reaction of 1, 2 or 3 equivalents of (diphenylphosphino)acetophenone, Ph2PCH2C(O)Ph (L), with in toluene afforded selectively 1, 2 or 3, respectively.Complex 1 hydrogenates and isomerises hex-1-ene at atmospheric hydrogen pressure, whereas 2 is inactive.Complex 3 exhibits a dynamic behaviour on the 1H NMR time-scale which corresponds to exchange between chelating and terminally bound phosphines.The activation energy of this process was calculated to be 63.7 +/- 0.7 kJ mol-1.Reaction of 3 with TIPF6 in CH2Cl2 gave 9 which reacted with a second equivalent of TIPF6 in MeCN to give the dicationic complex 10.The fac and mer isomers of the tris(enolato) Ru(II) complex 11a and 11b were obtained by reaction of 9 with NaH in tetrahydrofuran (thf).Treatment of 3 with NaOMe in toluene afforded selectively 11b, which has been crystallised by addition of 1,4,7,10,13-pentaoxacyclopentadecane (15-crown-5) to give 12.Protonation of 11b with HBF4*Et2O gave the neutral intermediate 13, characterised spectroscopically, and the final product 14.Treatment of with 2 equivalents of L yielded the ruthenium(III) complex 15, which was easily reduced to the ruthenium(II) complex 2.The solid state structures of complexes 2, 10 and 12 have been determined by single crystal X-ray analysis.The co-ordination of the metal in 2 and 10 is slightly distorted octahedral with the two phosphorous atoms (and oxygen atoms) in a cis position and the chloride and acetonitrile ligands, respectively, in a trans position.In the chiral anion of complex 12 the distorted octahedral structure has a meridional arrangement of the P atoms and electronic delocalisation occurs within the chelating phosphino enolate ligands.

View More

Products guided by the article

Product name:trans,cis,cis-[RuBr2((diphenylphosphino)acetophenone)2]

Cas No:162228-63-9

162228-63-9

R&D Labs maybe for 162228-63-9

Relevant to this article

Hot Product