cis-Diazido­[bis­(diphenyl­phosphino)methane-κ²P,P']ruthenium(II) dichloro­methane 0.42-solvate

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Complexes of some d and f elements with new 4-acylpyrazol-5-ones: synthesis and study

Complexes of 1-phenyl-3-methyl-4-thenoylpyrazol-5-one and of 1-phenyl-3-methyl-4-furancarbonylpyrazol-5-one, which was synthesized for the first time, with copper, rhodium, lanthanum, and europium were studied. The substances obtained were studied using, elemental analysis and IR spectroscopy, while the rhodium derivatives were additionally studied using the H-1 NMR method. The thermal stability of the copper derivatives was studied upon heating in a vacuum. The presence of additional heteroatoms in acylpyrazolone had virtually no effect on the structure and composition of the complexes formed. These ligands were shown to coordinate atoms of d and f metals through oxygen atoms similarly to other beta-diketones, whereas the remaining heteroatoms only participated in the formation of a hydrogen bonding system with additional ligands or coordinated solvent molecules

The reactivity of new (1,5-cyclooctadiene)rhodium acylpyrazolonates towards N- and P-donor ligands: X-ray structures of [Rh(1,5-COD)QS], [Rh(1,5-COD)(phen)]QS.0.5H2O (HQS = 1-phenyl-3-methyl-4-(2-thienoyl)-pyrazol-5-one) and [Rh(1,5-COD)Br]2

Complexes [Rh(1,5-COD)(Q)] have been prepared by the reaction between [Rh(1,5-COD)Cl](2) (1,5-COD = 1,5-cyclooetadiene) and HQ (where HQ = 1-phenyl-3-methyl-4-R-pyrazol-5-one: R = 2-thenoyl (HQ(s)), 2-furanoyl (HQ(o)) or tert-butylacetyl (HQ(T)). [Rh(1,5-COD)(Q)] react with N-2-donor ligands such as 1,10-phenanthroline (phen) or 2,2-bipyridyl (bipy) yielding ionic compounds [Rh(1,5-COD)(N-2-donor)]Q. The substitutional lability of 1,5-COD in [Rh(1,5-COD)(Q)] versus mono- and di-organophosphine ligands was also investigated. In all cases 1,5-COD has been displaced. Reaction with two equivalents of PPh3 gave, upon oxidation of the Rh(l) centre, [Rh(PPh3)1(01)(Q)l species containing a eta(2)-peroxo-group. Reaction of [Rh(1,5-COD)(Q)] with the chelating P-2-donor 1,2-bis(diphenylphosphino)ethane (dppe) or 4,4'-bis(diphenylphosphino)ferrocene (dppf) yields the peroxo Rh(III) compounds [Rh(dppe)(2)O-2]Q(T) and [Rh(dppf)O-2(Q(T))] or Rh(I) species [Rh(dppf-O-2)(Q(T))] containing the diphosphine in the oxidised form. Finally the reaction between [Rh(1,5-COD)(Q)] and allylbromide yields the well-known [Rh(1,5-COD)Br](2). All complexes have been characterised by analytical and spectral data (IR, H-1 and P-31 ((1)HJ-NMR spectra). The crystal structures of [Rh(1,5-COD)(Q(5))], [Rh(1,5-COD)(phen)]Q(5) and [Rh(1,5-COD)Br](2), all containing a Rh(l) atom in a square coordinate environment, are also reported. (C) 2002 Elsevier Science B.V. All rights reserved