Can a meso-type dinuclear complex be chiral?: dinuclear β-diketonato Ru(<scp>III</scp>) complexes

Sato, Hisako; Takase, Ryoichi; Mori, Yusuke; Yamagishi, Akihiko

doi:10.1039/c1dt11133g

Cited by 17 publications

(19 citation statements)

References 44 publications

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“…In this context, Sato et al investigated in detail the VCD spectra of tris (acetyl acetonate) complexes with different transition metal ions, 18 of their mixed ligand complexes, 19,20 and of larger multi-core complexes. [21][22][23] Recently, we carried out a systematic study on the VCD spectra of transition metal complexes of copper(II) and nickel(II) with the chiral diamine ligands, trans-1,2-diamino cyclohexane (chxn). 24 It was shown that the obtained VCD spectra feature characteristic differences between the tris-complexes of Ni (II) and Cu(II), and between the tris-and bis-complexes of Cu(II).…”

Section: Introductionmentioning

confidence: 99%

A comparative vibrational CD study of homo- and heteroleptic complexes of the type [Cu(trans-1,2-diaminocyclohexane)₂L](ClO₄)₂

Merten

2013

Dalton Trans.

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Vibrational circular dichroism (VCD) spectroscopy is a powerful tool to characterize absolute configurations and conformations of chiral organometallic systems. Such characterizations rely on the corresponding density functional theory (DFT) spectral simulations which may become very time consuming and sometimes even impossible for systems with increasing complexity. Systematic studies on small model compounds can lead to empirical structure-spectra relationships. The present work continues the systematic investigations of transition metal complexes of chiral trans-1,2-diamino-cyclohexane (chxn). VA and VCD spectra of the mixed-ligand complexes [Cu(chxn)2L](2+) with L being either ethylene diamine (en) or N,N'-dimethylethylene diamine (dmen) are measured. The comparison of the experimental spectra of the mixed-ligand complexes with those of the distorted octahedral complex [Cu(chxn)3](2+) reveals that the VA and VCD patterns below 1500 cm(-1) of the three complexes are not significantly affected by the nature of the third ligand, while the VCD pattern of the NH2-bending modes in the 1500 to 1800 cm(-1) region features some characteristic changes. Comparison with the corresponding DFT spectral calculations shows that these spectral differences are related to the relative abundance of the Δ- and Λ-configurations at the metal ion. In addition, the results of this study highlight that the VCD pattern of the NH2-bending modes is characteristic of the coordination number and the configuration of the metal center.

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Section: Introductionmentioning

confidence: 99%

A comparative vibrational CD study of homo- and heteroleptic complexes of the type [Cu(trans-1,2-diaminocyclohexane)₂L](ClO₄)₂

Merten

2013

Dalton Trans.

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“…Heterometallic oligomers were prepared by connecting bis(β-diketonato)ruthenium(III) moieties to a labile metal ion through bis-β-diketonato bridging ligands [19,21,22,52,53]. The main attention is focused on the possibility of the induction of chiral coordination structures around the labile metal ion.…”

Section: Vcd Application To Oligomers Of Chiral Metal Complexes Inmentioning

confidence: 99%

“…In this section, we report the chiral induction of a bridging part by use of an non-symmetrical β-diketonato ligand, in which the twisting of two β-diketonato planes causes C 2 symmetry [21,24]. …”

Section: Vcd Application To Oligomers Of Chiral Metal Complexes Inmentioning

confidence: 99%

“…Solid and dotted lines correspond to less and more retained enantiomers, respectively. It should be noted that the peak intensity for the meso-type dimers is ten times lower than that for the racemic dimers (modified from [21]).…”

Section: Figurementioning

confidence: 99%

“…Structures of ( a ) 1,2-diacetyl-1,2-dibenzoylethane (dabeH 2 ) and ( b ) [Ru(III)(acac) 2 (dabe)Ru(III)(acac) 2 ] (modified from [21]).…”

Section: Figurementioning

confidence: 99%

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VCD Studies on Chiral Characters of Metal Complex Oligomers

Sato

Yamagishi

2013

IJMS

Self Cite

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The present article reviews the results on the application of vibrational circular dichroism (VCD) spectroscopy to the study of stereochemical properties of chiral metal complexes in solution. The chiral characters reflecting on the vibrational properties of metal complexes are revealed by measurements of a series of β-diketonato complexes with the help of theoretical calculation. Attention is paid to the effects of electronic properties of a central metal ion on vibrational energy levels or low-lying electronic states. The investigation is further extended to the oligomers of β-diketonato complex units. The induction of chiral structures is confirmed by the VCD spectra when chiral inert moieties are connected with labile metal ions. These results have demonstrated how VCD spectroscopy is efficient in revealing the static and dynamic properties of mononuclear and multinuclear chiral metal complexes, which are difficult to clarify by means of other spectroscopes.

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Mid‐IR and CH stretching vibrational circular dichroism spectroscopy to distinguish various sources of chirality: The case of quinophaneoxazoline based ruthenium(II) complexes

Fusè,

Mazzeo,

Abbate

et al. 2024

Chirality

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Five diastereomers of ruthenium(II) complexes based on quinolinophaneoxazoline ligands were investigated by vibrational circular dichroism (VCD) in the mid‐IR and CH stretching regions. Diastereomers differ in three sources of chirality: the planar chirality of the quinolinophane moiety, the central chirality of an asymmetric carbon atom of the oxazoline ring, and the chirality of the ruthenium atom. VCD, allied to DFT calculations, has been found to be effective in disentangling the various forms of chirality. In particular, a VCD band is identified in the CH stretching region directly connected to the chirality of the metal. The analysis of the calculated VCD spectra is carried out by partitioning the complexes into fragments. The anharmonic analysis is also performed with a recently proposed reduced‐dimensionality approach: such treatment is particularly important when examining spectroscopic regions highly perturbed by resonances, like the CH stretching region.

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Can a meso-type dinuclear complex be chiral?: dinuclear β-diketonato Ru(III) complexes

Cited by 17 publications

References 44 publications

A comparative vibrational CD study of homo- and heteroleptic complexes of the type [Cu(trans-1,2-diaminocyclohexane)₂L](ClO₄)₂

A comparative vibrational CD study of homo- and heteroleptic complexes of the type [Cu(trans-1,2-diaminocyclohexane)₂L](ClO₄)₂

VCD Studies on Chiral Characters of Metal Complex Oligomers

Mid‐IR and CH stretching vibrational circular dichroism spectroscopy to distinguish various sources of chirality: The case of quinophaneoxazoline based ruthenium(II) complexes

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Can a meso-type dinuclear complex be chiral?: dinuclear β-diketonato Ru(III) complexes

Cited by 17 publications

References 44 publications

A comparative vibrational CD study of homo- and heteroleptic complexes of the type [Cu(trans-1,2-diaminocyclohexane)2L](ClO4)2

A comparative vibrational CD study of homo- and heteroleptic complexes of the type [Cu(trans-1,2-diaminocyclohexane)2L](ClO4)2

VCD Studies on Chiral Characters of Metal Complex Oligomers

Mid‐IR and CH stretching vibrational circular dichroism spectroscopy to distinguish various sources of chirality: The case of quinophaneoxazoline based ruthenium(II) complexes

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A comparative vibrational CD study of homo- and heteroleptic complexes of the type [Cu(trans-1,2-diaminocyclohexane)₂L](ClO₄)₂

A comparative vibrational CD study of homo- and heteroleptic complexes of the type [Cu(trans-1,2-diaminocyclohexane)₂L](ClO₄)₂