Mechanism and activation parameters for the κ O to μ, κ2 O, O′ bonding mode of the maleic acid ligand on an osmium carbonyl cluster

Rakesh Ganguly; Leong Weng Kee

doi:10.1021/om200119z

Mechanism and activation parameters for the κ O to μ, κ² O, O′ bonding mode of the maleic acid ligand on an osmium carbonyl cluster

Rakesh Ganguly, Leong Weng Kee^*

^*Corresponding author for this work

Nanyang Technological University

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

4 Citations (Scopus)

Abstract

The reaction of maleic acid and [Os₃(CO)₁₀(NCCH ₃)₂] afforded initially the cluster [Os ₃(μ-H)(CO)₁₀(O₂CCH=CHCO₂H) (CH₃CN)], in which the maleic acid was κO bonded. This slowly converted to [Os₃(μ-H)(CO)₁₀(μ-O₂CCH= CHCO₂H)], in which the ligand adopted the more usual μ,κ²O,O′ bonding mode. The conversion was followed by monitoring the metal hydride resonance in the ¹H NMR spectrum, and analysis of the data yielded ΔH^† = 110 ± 3 kJ mol^-1 and ΔS^† = 14 ± 10 J mol ^-1 K^-1 for this process, thus suggesting an I_D mechanism. The calculated values are in good agreement with the experimental values.

Original language	English
Pages (from-to)	3966-3970
Number of pages	5
Journal	Organometallics
Volume	30
Issue number	15
DOIs	https://doi.org/10.1021/om200119z
Publication status	Published - Aug 8 2011
Externally published	Yes

ASJC Scopus Subject Areas

Physical and Theoretical Chemistry
Organic Chemistry
Inorganic Chemistry

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@article{20d880cdbc8c47ea9c3fee4751ca19da,

title = "Mechanism and activation parameters for the κ O to μ, κ2 O, O′ bonding mode of the maleic acid ligand on an osmium carbonyl cluster",

abstract = "The reaction of maleic acid and [Os3(CO)10(NCCH 3)2] afforded initially the cluster [Os 3(μ-H)(CO)10(O2CCH=CHCO2H) (CH3CN)], in which the maleic acid was κO bonded. This slowly converted to [Os3(μ-H)(CO)10(μ-O2CCH= CHCO2H)], in which the ligand adopted the more usual μ,κ2O,O′ bonding mode. The conversion was followed by monitoring the metal hydride resonance in the 1H NMR spectrum, and analysis of the data yielded ΔH† = 110 ± 3 kJ mol-1 and ΔS† = 14 ± 10 J mol -1 K-1 for this process, thus suggesting an ID mechanism. The calculated values are in good agreement with the experimental values.",

author = "Rakesh Ganguly and Kee, {Leong Weng}",

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journal = "Organometallics",

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T1 - Mechanism and activation parameters for the κ O to μ, κ2 O, O′ bonding mode of the maleic acid ligand on an osmium carbonyl cluster

AU - Ganguly, Rakesh

AU - Kee, Leong Weng

PY - 2011/8/8

Y1 - 2011/8/8

N2 - The reaction of maleic acid and [Os3(CO)10(NCCH 3)2] afforded initially the cluster [Os 3(μ-H)(CO)10(O2CCH=CHCO2H) (CH3CN)], in which the maleic acid was κO bonded. This slowly converted to [Os3(μ-H)(CO)10(μ-O2CCH= CHCO2H)], in which the ligand adopted the more usual μ,κ2O,O′ bonding mode. The conversion was followed by monitoring the metal hydride resonance in the 1H NMR spectrum, and analysis of the data yielded ΔH† = 110 ± 3 kJ mol-1 and ΔS† = 14 ± 10 J mol -1 K-1 for this process, thus suggesting an ID mechanism. The calculated values are in good agreement with the experimental values.

AB - The reaction of maleic acid and [Os3(CO)10(NCCH 3)2] afforded initially the cluster [Os 3(μ-H)(CO)10(O2CCH=CHCO2H) (CH3CN)], in which the maleic acid was κO bonded. This slowly converted to [Os3(μ-H)(CO)10(μ-O2CCH= CHCO2H)], in which the ligand adopted the more usual μ,κ2O,O′ bonding mode. The conversion was followed by monitoring the metal hydride resonance in the 1H NMR spectrum, and analysis of the data yielded ΔH† = 110 ± 3 kJ mol-1 and ΔS† = 14 ± 10 J mol -1 K-1 for this process, thus suggesting an ID mechanism. The calculated values are in good agreement with the experimental values.

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Mechanism and activation parameters for the κ O to μ, κ² O, O′ bonding mode of the maleic acid ligand on an osmium carbonyl cluster

Abstract

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