The trans-Effect in Octahedral Complexes. VI. Base Hydrolysis of trans-Hydroxybromo and trans-Hydroxychlorobis(ethylenediamine)-rhodium(III) Complexes

Poë, Anthony J.; Vuik, Carol P. J.

doi:10.1139/v75-256

Cited by 7 publications

(1 citation statement)

References 10 publications

(14 reference statements)

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“…This method allows for a greater number of degrees of freedom, N − n , to be used in the estimates of σ( k obs ), and, therefore, smaller “student's t ” factors are used to calculate any particular confidence level. The constant percentage uncertainty irrespective of temperature has been shown elsewhere to be generally valid . This is equivalent to assuming a constant absolute error in ln( k obs / T ), an assumption implicit in all unweighted least-squares Eyring analyses.…”

Section: Discussionmentioning

confidence: 92%

Chelation Kinetics of Bidentate Phosphine Ligands on Pentacoordinate Ruthenium Carbonyl Complexes

et al. 2000

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Chelation kinetics of the complexes Ru(CO) 4 (η 1 -(P-P)) have been studied in heptane, where P-P ) Ph 2 P(CH 2 ) n PPh 2 (n ) 1, 2, 3, or 4, i.e., dppm, dppe, dppp, or dppb), Ph 2 P(NMe)PPh 2 (dppma), Ph 2 P(o-C 6 H 4 )PPh 2 (dpp-benzene), or R 2 P(CH 2 ) 2 PR 2 (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 (C 2 H 4 ), which itself was prepared in situ by photolysis of Ru 3 (CO) 12 under C 2 H 4 . The initially formed Ru(CO) 4 (η 1 -(P-P)) complexes react cleanly to form axial-equatorial Ru-(CO) 3 (η 2 -(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 Ru 2 -(CO) 3 (µ-PPh 2 )(µ-Ph 2 PNMePPh 2 ). The kinetics of the displacement of CO from Ru(CO) 4 (η 1 -(P-P)) in n-heptane are characterized by ∆H q values that are lower by up to 9 kcal mol -1 than those of their monodentate P-donor analogues. ∆S q 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 < dcpe < dmpe < dppp e dppm ≈ dppbu ≈ dppe , dppma. This contrasts with the CO-dissociative reactions of analogous Ru(CO) 4 L complexes when L ) monodentate P-donor ligands.

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Section: Discussionmentioning

confidence: 92%

Chelation Kinetics of Bidentate Phosphine Ligands on Pentacoordinate Ruthenium Carbonyl Complexes

et al. 2000

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Ligand Substitution Dynamics in Metal Complexes

Swaddle

2010

Physical Inorganic Chemistry

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On the base of our previous studies due to the presence of halides in our complexes there is strong probability for obtaining coordination polymers. Crystal engineering well-defined as the understanding of intermolecular interactions in the context of crystal packing and the utilization of such understanding in the design of new solids with desired physical and chemical properties. Owing to the fact that the small changes in the ligands may play a significant role in the complexes, the organic ligand (1-naphtyl pyridine-2-carboxylate) (L), was synthesized. In order make more steric repulsion around of the complexes resulted in the substitution effect around of the naphtyl moiety was hired in the design. Relocation in the position of functional group was fulfilled our expectations. Three new mercury (II) halide complexes, [Hg(L)2Cl2] (1), [Hg(L)2Br2] (2) and [Hg(L)2I2] (3) were synthesized. All of the compounds were fully characterized using FT-IR, TGA, DSC, mass spectrometry, CHNOS elemental analyses, PXRD, NMR and SCXRD. The results indicate that metal-ligand polymerization controlled by substitution effect. The coordination geometry around the Hg (II) ion is seesaw shape in distorted tetrahedral geometry for compounds (1), (2) and (3) with τ4 of 0.74, 0.76 and 0.78, respectively. Due to the replacement of the functional group (mentioned substitution effect), flexibility of coodinated ligand was decreased. In the previously reported structures, the angle between two planes of aromatic rings in the analogous ligand was 78.37o which changed to the 59.47o, 50.75o and 64.90o for mercury halide series complexes. In present study these angles are 89.09, 89.73 and 88.90 for titled complexes based on new designed ligand. Consequently, this study emphasize that the substitution effect can play the significant role through the flexibility of designed ligand to control the metal-ligand polymerization.

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ChemInform Abstract: THE TRANS-EFFECT IN OCTAHEDRAL COMPLEXES PART 6, BASE HYDROLYSIS OF TRANS-HYDROXYBROMO AND TRANS-HYDROXYCHLOROBIS(ETHYLENEDIAMINE)-RHODIUM(III) COMPLEXES

Poë¹,

Vuik²

1975

Chemischer Informationsdienst

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The trans-Effect in Octahedral Complexes. VI. Base Hydrolysis of trans-Hydroxybromo and trans-Hydroxychlorobis(ethylenediamine)-rhodium(III) Complexes

Cited by 7 publications

References 10 publications

Chelation Kinetics of Bidentate Phosphine Ligands on Pentacoordinate Ruthenium Carbonyl Complexes

Chelation Kinetics of Bidentate Phosphine Ligands on Pentacoordinate Ruthenium Carbonyl Complexes

Ligand Substitution Dynamics in Metal Complexes

ChemInform Abstract: THE TRANS-EFFECT IN OCTAHEDRAL COMPLEXES PART 6, BASE HYDROLYSIS OF TRANS-HYDROXYBROMO AND TRANS-HYDROXYCHLOROBIS(ETHYLENEDIAMINE)-RHODIUM(III) COMPLEXES

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