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Ligand substitution kinetics in M(CO)(4)(eta(2 : 2)-1,5-cyclooctadiene) complexes (M = Cr, Mo, W) - substitution of 1,5-cyclooctadiene by bis(diphenylphosphino)alkanes
Date
1999-01-30
Author
Kayran, C
Kozanoglu, F
Özkar, Saim
Saldamli, S
Tekkaya, A
Kreiter, CG
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The thermal substitution kinetics of 1,5-cyclooctadiene (COD) by bis(diphenylphosphino)alkanes (PP), (C6H5)(2)P(CH2)(n)P(C6H5)(2) (n = 1, 2, 3) in M(CO)(4)(eta(2:2)-COD) complexes (M = Cr, Mo, W), were studied by quantitative FT-LR spectroscopy. The reaction rate exhibits first-order dependence on the concentration of the starting complex, and the observed rate constant depends on the concentration of the leaving COD ligand and on the concentration and the nature of the entering PP ligand. In the proposed mechanism. the rate determining step is the cleavage of one metal-olefin bond of the COD ligand. A rate-law is derived from the proposed mechanism. The evaluation of the kinetic data gives the activation parameters which support an associative mechanism in the transition states. Both the observed rare constant and the activation parameters show little variation with the chain length of the diphosphine ligand. (C) 1999 Elsevier Science S.A. All rights reserved.
Subject Keywords
Ligand Substitution
,
Molybdenum Complexes
,
Tungsten Complexes
,
Diphosphine Complexes
,
Kinetics And Mechanism
URI
https://hdl.handle.net/11511/42687
Journal
INORGANICA CHIMICA ACTA
DOI
https://doi.org/10.1016/s0020-1693(98)00293-x
Collections
Department of Chemistry, Article