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]

Atsushi Inatomi; Masaaki Abe; Yoshio Hisaeda

doi:10.1071/CH12378

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]

Atsushi Inatomi, Masaaki Abe, Yoshio Hisaeda

Research output: Contribution to journal › Article › peer-review

6 Citations (Scopus)

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 k_ex^298K=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.

Original language	English
Pages (from-to)	1599-1607
Number of pages	9
Journal	Australian Journal of Chemistry
Volume	65
Issue number	12
DOIs	https://doi.org/10.1071/CH12378
Publication status	Published - 2012

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Chemistry(all)

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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]. / Inatomi, Atsushi; Abe, Masaaki; Hisaeda, Yoshio.

In: Australian Journal of Chemistry, Vol. 65, No. 12, 2012, p. 1599-1607.

Research output: Contribution to journal › Article › peer-review

@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",

note = "Funding Information: This work was supported by Grants-in-Aid for Scientific Research on Innovative Areas {\textquoteleft}Coordination Programming{\textquoteright} (No. 22108523) and {\textquoteleft}Molecular Activation{\textquoteright} (No. 23105537), Grants-in-Aid for Scientific Research (A) (No. 21245016) and (B) (No. 20350029), Grant-in-Aid for Challenging Exploratory Research (No. 24655134), Grant-in-Aid for JSPS Fellow, and the Global COE Program {\textquoteleft}Science for Future Molecular Systems{\textquoteright} from MEXT.",

year = "2012",

doi = "10.1071/CH12378",

language = "English",

volume = "65",

pages = "1599--1607",

journal = "Australian Journal of Chemistry",

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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

N1 - Funding Information: This work was supported by Grants-in-Aid for Scientific Research on Innovative Areas ‘Coordination Programming’ (No. 22108523) and ‘Molecular Activation’ (No. 23105537), Grants-in-Aid for Scientific Research (A) (No. 21245016) and (B) (No. 20350029), Grant-in-Aid for Challenging Exploratory Research (No. 24655134), Grant-in-Aid for JSPS Fellow, and the Global COE Program ‘Science for Future Molecular Systems’ from MEXT.

PY - 2012

Y1 - 2012

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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