Syntheses and properties of a series of oxo-centered triruthenium complexes with thiocyanate and nitrite as terminal ligand

Hiroyoshi Ohtsu; Naoki Oka; Tadashi Yamaguchi

doi:10.1016/j.ica.2011.08.031

Syntheses and properties of a series of oxo-centered triruthenium complexes with thiocyanate and nitrite as terminal ligand

Hiroyoshi Ohtsu, Naoki Oka, Tadashi Yamaguchi^*

^*Corresponding author for this work

School of Advanced Science and Engineering

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

7 Citations (Scopus)

Abstract

Six new oxo-centered triruthenium complexes with NCS ^- or NO ₂ ^- as a terminal ligand [Ru ₃O(CH ₃CO ₂) ₆(NCS)(L) ₂] {L = 4-dimethylaminopyridine (dmap) (1); L = pyridine (py) (2)}, [PPh ₄] ₂[Ru ₃O(CH ₃CO ₂) ₆(NCS) ₃] (3), [PPh ₄] ₂[Ru ₃O(CH ₃CO ₂) ₆(CO)(NCS) ₂] (4), and [Ru ₃O(CH ₃CO ₂) ₆(NO ₂)(L) ₂] {L = dmap (5); L = py (6)} were prepared. The thiocyanate is coordinated through N atom for all NCS ^- complexes. While dmap complex 5 was obtained as single isomer with N-coordinate nitrite, py complex 6 was obtained as a mixture of two isomers involving coordination mode of nitrite. The linkage isomerization is too fast to allow separation of these isomers and it was confirmed by saturation transfer technique on ¹H NMR. These compounds show reversible redox behavior and the redox potentials suggest that these anionic ligands are slightly electron donating than pyridine derivatives. Crystal structures of [Ru ₃O(CH ₃CO ₂) ₆(NCS)(C ₅H ₅N) ₂] ·2CH ₂Cl ₂ were determined by X-ray crystallography. Although the complex has mixed terminal ligand, the Ru ₃O core is almost equilateral.

Original language	English
Pages (from-to)	1-6
Number of pages	6
Journal	Inorganica Chimica Acta
Volume	383
DOIs	https://doi.org/10.1016/j.ica.2011.08.031
Publication status	Published - 2012 Mar 30

Keywords

Cluster compounds
Linkage isomer
Ruthenium complexes

ASJC Scopus subject areas

Physical and Theoretical Chemistry
Inorganic Chemistry
Materials Chemistry

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10.1016/j.ica.2011.08.031

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title = "Syntheses and properties of a series of oxo-centered triruthenium complexes with thiocyanate and nitrite as terminal ligand",

abstract = "Six new oxo-centered triruthenium complexes with NCS - or NO 2 - as a terminal ligand [Ru 3O(CH 3CO 2) 6(NCS)(L) 2] {L = 4-dimethylaminopyridine (dmap) (1); L = pyridine (py) (2)}, [PPh 4] 2[Ru 3O(CH 3CO 2) 6(NCS) 3] (3), [PPh 4] 2[Ru 3O(CH 3CO 2) 6(CO)(NCS) 2] (4), and [Ru 3O(CH 3CO 2) 6(NO 2)(L) 2] {L = dmap (5); L = py (6)} were prepared. The thiocyanate is coordinated through N atom for all NCS - complexes. While dmap complex 5 was obtained as single isomer with N-coordinate nitrite, py complex 6 was obtained as a mixture of two isomers involving coordination mode of nitrite. The linkage isomerization is too fast to allow separation of these isomers and it was confirmed by saturation transfer technique on 1H NMR. These compounds show reversible redox behavior and the redox potentials suggest that these anionic ligands are slightly electron donating than pyridine derivatives. Crystal structures of [Ru 3O(CH 3CO 2) 6(NCS)(C 5H 5N) 2] ·2CH 2Cl 2 were determined by X-ray crystallography. Although the complex has mixed terminal ligand, the Ru 3O core is almost equilateral.",

keywords = "Cluster compounds, Linkage isomer, Ruthenium complexes",

author = "Hiroyoshi Ohtsu and Naoki Oka and Tadashi Yamaguchi",

year = "2012",

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doi = "10.1016/j.ica.2011.08.031",

language = "English",

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journal = "Inorganica Chimica Acta",

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T1 - Syntheses and properties of a series of oxo-centered triruthenium complexes with thiocyanate and nitrite as terminal ligand

AU - Ohtsu, Hiroyoshi

AU - Oka, Naoki

AU - Yamaguchi, Tadashi

PY - 2012/3/30

Y1 - 2012/3/30

N2 - Six new oxo-centered triruthenium complexes with NCS - or NO 2 - as a terminal ligand [Ru 3O(CH 3CO 2) 6(NCS)(L) 2] {L = 4-dimethylaminopyridine (dmap) (1); L = pyridine (py) (2)}, [PPh 4] 2[Ru 3O(CH 3CO 2) 6(NCS) 3] (3), [PPh 4] 2[Ru 3O(CH 3CO 2) 6(CO)(NCS) 2] (4), and [Ru 3O(CH 3CO 2) 6(NO 2)(L) 2] {L = dmap (5); L = py (6)} were prepared. The thiocyanate is coordinated through N atom for all NCS - complexes. While dmap complex 5 was obtained as single isomer with N-coordinate nitrite, py complex 6 was obtained as a mixture of two isomers involving coordination mode of nitrite. The linkage isomerization is too fast to allow separation of these isomers and it was confirmed by saturation transfer technique on 1H NMR. These compounds show reversible redox behavior and the redox potentials suggest that these anionic ligands are slightly electron donating than pyridine derivatives. Crystal structures of [Ru 3O(CH 3CO 2) 6(NCS)(C 5H 5N) 2] ·2CH 2Cl 2 were determined by X-ray crystallography. Although the complex has mixed terminal ligand, the Ru 3O core is almost equilateral.

AB - Six new oxo-centered triruthenium complexes with NCS - or NO 2 - as a terminal ligand [Ru 3O(CH 3CO 2) 6(NCS)(L) 2] {L = 4-dimethylaminopyridine (dmap) (1); L = pyridine (py) (2)}, [PPh 4] 2[Ru 3O(CH 3CO 2) 6(NCS) 3] (3), [PPh 4] 2[Ru 3O(CH 3CO 2) 6(CO)(NCS) 2] (4), and [Ru 3O(CH 3CO 2) 6(NO 2)(L) 2] {L = dmap (5); L = py (6)} were prepared. The thiocyanate is coordinated through N atom for all NCS - complexes. While dmap complex 5 was obtained as single isomer with N-coordinate nitrite, py complex 6 was obtained as a mixture of two isomers involving coordination mode of nitrite. The linkage isomerization is too fast to allow separation of these isomers and it was confirmed by saturation transfer technique on 1H NMR. These compounds show reversible redox behavior and the redox potentials suggest that these anionic ligands are slightly electron donating than pyridine derivatives. Crystal structures of [Ru 3O(CH 3CO 2) 6(NCS)(C 5H 5N) 2] ·2CH 2Cl 2 were determined by X-ray crystallography. Although the complex has mixed terminal ligand, the Ru 3O core is almost equilateral.

KW - Cluster compounds

KW - Linkage isomer

KW - Ruthenium complexes

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JO - Inorganica Chimica Acta

JF - Inorganica Chimica Acta

ER -

Syntheses and properties of a series of oxo-centered triruthenium complexes with thiocyanate and nitrite as terminal ligand

Abstract

Keywords

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