Oxo-centred trimetallic clusters supported by electron-withdrawing carboxylates: Highly inert character in ligand exchange kinetics of the dichloroacetate-bridged complex [Ru33-O)(μ- CHCl2COO)6(pyridine)3]

Atsushi Inatomi, Masaaki Abe, Yoshio Hisaeda

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Abstract

Two new oxo-centred trinuclear ruthenium clusters supported by six dichloroacetate ligands, [Ru33-O)(μ-CHCl 2COO)6(CH3OH)3]CHCl2COO (1) and [Ru33-O)(μ-CHCl2COO)6(pyridine) 3] (2), have been synthesised and characterised by spectroscopic methods, electrospray ionisation mass spectrometry, single-crystal X-ray diffraction, and cyclic voltammetry. Due to the strong inductive effect of the dichloroacetate ligands, the redox potential of 2 was shifted to the positive side (∼1.0V or more) relative to the acetate analogue [Ru33-O) (μ-CH3COO)6(pyridine)3], and also the rate of pyridine/pyridine-d5 exchange reaction of 2 in CD3CN was retarded with the rate constant of kex298K=1. 9×10-8s-1 which is 105-fold smaller than the value for [Ru33-O)(μ-CH3COO) 6(pyridine)3]. Highly positive activation parameters obtained for 2, ΔH=138±7kJmol-1 and ΔS=71±20JK-1mol-1, illustrate a dissociative activation pathway in which rupture of the Ru-N(pyridine) bond is involved in the rate-determining step.

Original languageEnglish
Pages (from-to)1599-1607
Number of pages9
JournalAustralian Journal of Chemistry
Volume65
Issue number12
DOIs
Publication statusPublished - Dec 31 2012

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Ligands
Kinetics
Electrons
Chemical activation
Electrospray ionization
Ruthenium
Cyclic voltammetry
Mass spectrometry
pyridine
Rate constants
Acetates
Single crystals
X ray diffraction

All Science Journal Classification (ASJC) codes

  • Chemistry(all)

Cite this

@article{51bfc25120c14f0e9c0383e5b6a03fac,
title = "Oxo-centred trimetallic clusters supported by electron-withdrawing carboxylates: Highly inert character in ligand exchange kinetics of the dichloroacetate-bridged complex [Ru3(μ3-O)(μ- CHCl2COO)6(pyridine)3]",
abstract = "Two new oxo-centred trinuclear ruthenium clusters supported by six dichloroacetate ligands, [Ru3(μ3-O)(μ-CHCl 2COO)6(CH3OH)3]CHCl2COO (1) and [Ru3(μ3-O)(μ-CHCl2COO)6(pyridine) 3] (2), have been synthesised and characterised by spectroscopic methods, electrospray ionisation mass spectrometry, single-crystal X-ray diffraction, and cyclic voltammetry. Due to the strong inductive effect of the dichloroacetate ligands, the redox potential of 2 was shifted to the positive side (∼1.0V or more) relative to the acetate analogue [Ru3(μ3-O) (μ-CH3COO)6(pyridine)3], and also the rate of pyridine/pyridine-d5 exchange reaction of 2 in CD3CN was retarded with the rate constant of kex298K=1. 9×10-8s-1 which is 105-fold smaller than the value for [Ru3(μ3-O)(μ-CH3COO) 6(pyridine)3]. Highly positive activation parameters obtained for 2, ΔH‡=138±7kJmol-1 and ΔS‡=71±20JK-1mol-1, illustrate a dissociative activation pathway in which rupture of the Ru-N(pyridine) bond is involved in the rate-determining step.",
author = "Atsushi Inatomi and Masaaki Abe and Yoshio Hisaeda",
year = "2012",
month = "12",
day = "31",
doi = "10.1071/CH12378",
language = "English",
volume = "65",
pages = "1599--1607",
journal = "Australian Journal of Chemistry",
issn = "0004-9425",
publisher = "CSIRO",
number = "12",

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T1 - Oxo-centred trimetallic clusters supported by electron-withdrawing carboxylates

T2 - Highly inert character in ligand exchange kinetics of the dichloroacetate-bridged complex [Ru3(μ3-O)(μ- CHCl2COO)6(pyridine)3]

AU - Inatomi, Atsushi

AU - Abe, Masaaki

AU - Hisaeda, Yoshio

PY - 2012/12/31

Y1 - 2012/12/31

N2 - Two new oxo-centred trinuclear ruthenium clusters supported by six dichloroacetate ligands, [Ru3(μ3-O)(μ-CHCl 2COO)6(CH3OH)3]CHCl2COO (1) and [Ru3(μ3-O)(μ-CHCl2COO)6(pyridine) 3] (2), have been synthesised and characterised by spectroscopic methods, electrospray ionisation mass spectrometry, single-crystal X-ray diffraction, and cyclic voltammetry. Due to the strong inductive effect of the dichloroacetate ligands, the redox potential of 2 was shifted to the positive side (∼1.0V or more) relative to the acetate analogue [Ru3(μ3-O) (μ-CH3COO)6(pyridine)3], and also the rate of pyridine/pyridine-d5 exchange reaction of 2 in CD3CN was retarded with the rate constant of kex298K=1. 9×10-8s-1 which is 105-fold smaller than the value for [Ru3(μ3-O)(μ-CH3COO) 6(pyridine)3]. Highly positive activation parameters obtained for 2, ΔH‡=138±7kJmol-1 and ΔS‡=71±20JK-1mol-1, illustrate a dissociative activation pathway in which rupture of the Ru-N(pyridine) bond is involved in the rate-determining step.

AB - Two new oxo-centred trinuclear ruthenium clusters supported by six dichloroacetate ligands, [Ru3(μ3-O)(μ-CHCl 2COO)6(CH3OH)3]CHCl2COO (1) and [Ru3(μ3-O)(μ-CHCl2COO)6(pyridine) 3] (2), have been synthesised and characterised by spectroscopic methods, electrospray ionisation mass spectrometry, single-crystal X-ray diffraction, and cyclic voltammetry. Due to the strong inductive effect of the dichloroacetate ligands, the redox potential of 2 was shifted to the positive side (∼1.0V or more) relative to the acetate analogue [Ru3(μ3-O) (μ-CH3COO)6(pyridine)3], and also the rate of pyridine/pyridine-d5 exchange reaction of 2 in CD3CN was retarded with the rate constant of kex298K=1. 9×10-8s-1 which is 105-fold smaller than the value for [Ru3(μ3-O)(μ-CH3COO) 6(pyridine)3]. Highly positive activation parameters obtained for 2, ΔH‡=138±7kJmol-1 and ΔS‡=71±20JK-1mol-1, illustrate a dissociative activation pathway in which rupture of the Ru-N(pyridine) bond is involved in the rate-determining step.

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