Experimental and theoretical aspects of the haptotropic rearrangement of diiron and diruthenium carbonyl complexes bound to 4,6,8-trimethylazulene

Kazuhiro Tsuchiya, Keiko Ideta, Koichi Mogi, Yusuke Sunada, Hideo Nagashima

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Abstract

The haptotropic rearrangement of dinuclear metal carbonyl species on the conjugate π-ligand of (μ235- 4,6,8-trimethylazulene)M2(CO)5 [M = Fe (3) and Ru (4)] was investigated in detail both experimentally and theoretically. The complexes, 3 and 4, were synthesized and characterized by spectroscopy and crystallography. The spin saturation transfer technique of 1H NMR was used to measure the rate constant k of the haptotropic isomerization between the two enantiomers of 3 and 4, from which thermodynamic parameters were determined: (3; ΔS = -7 ± 1 cal K-1 mol-1, ΔH = 22 ± 1 cal mol-1, ΔG 373 = 25 ± 1 cal mol-1), (4; ΔS = 7 ± 1 cal K-1 mol-1, ΔH = 25 ± 1 cal mol-1, ΔG 373 = 23 ± 1 cal mol-1). DFT calculations (the B3LYP, B1B95 and PBE1PBE methods) were also carried out using the CEP-31G and cc-pVDZ as the basis set of the transition metal and other elements, respectively, by which both ground state and transition state structures were optimized for the haptotropic rearrangement of 3 and 4. The potential energy surface for these reactions suggests that the reaction involves the conversion of the coordination mode from μ2, η35- (ground state) to μ2, η15- (transition state). Mechanistic consideration, in particular that of differences in transition states between the diiron and diruthenium complexes, is also described.

Original languageEnglish
Pages (from-to)2708-2716
Number of pages9
JournalDalton Transactions
Issue number20
DOIs
Publication statusPublished - Jul 17 2008

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Electron transitions
Ground state
Potential energy surfaces
Crystallography
Enantiomers
Carbon Monoxide
Isomerization
Discrete Fourier transforms
Chemical elements
Transition metals
Rate constants
Metals
Nuclear magnetic resonance
Spectroscopy
Thermodynamics
Ligands
benzmetanide

All Science Journal Classification (ASJC) codes

  • Inorganic Chemistry

Cite this

Experimental and theoretical aspects of the haptotropic rearrangement of diiron and diruthenium carbonyl complexes bound to 4,6,8-trimethylazulene. / Tsuchiya, Kazuhiro; Ideta, Keiko; Mogi, Koichi; Sunada, Yusuke; Nagashima, Hideo.

In: Dalton Transactions, No. 20, 17.07.2008, p. 2708-2716.

Research output: Contribution to journalArticle

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AB - The haptotropic rearrangement of dinuclear metal carbonyl species on the conjugate π-ligand of (μ2,η3:η5- 4,6,8-trimethylazulene)M2(CO)5 [M = Fe (3) and Ru (4)] was investigated in detail both experimentally and theoretically. The complexes, 3 and 4, were synthesized and characterized by spectroscopy and crystallography. The spin saturation transfer technique of 1H NMR was used to measure the rate constant k of the haptotropic isomerization between the two enantiomers of 3 and 4, from which thermodynamic parameters were determined: (3; ΔS‡ = -7 ± 1 cal K-1 mol-1, ΔH‡ = 22 ± 1 cal mol-1, ΔG ‡373 = 25 ± 1 cal mol-1), (4; ΔS‡ = 7 ± 1 cal K-1 mol-1, ΔH‡ = 25 ± 1 cal mol-1, ΔG ‡373 = 23 ± 1 cal mol-1). DFT calculations (the B3LYP, B1B95 and PBE1PBE methods) were also carried out using the CEP-31G and cc-pVDZ as the basis set of the transition metal and other elements, respectively, by which both ground state and transition state structures were optimized for the haptotropic rearrangement of 3 and 4. The potential energy surface for these reactions suggests that the reaction involves the conversion of the coordination mode from μ2, η3,η5- (ground state) to μ2, η1,η5- (transition state). Mechanistic consideration, in particular that of differences in transition states between the diiron and diruthenium complexes, is also described.

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