A square-planar nickel(II) monoradical complex with a bis(salicylidene)- diamine ligand

Laurent Benisvy; Ramu Kannappan; Yu Fei Song; Sergey Milikisyants; Martina Huber; Ilpo Mutikainen; Urho Turpeinen; Patrick Gamez; Leonardo Bernasconi; Evert Jan Baerends; František Hartl; Jan Reedijk

doi:10.1002/ejic.200601015

A square-planar nickel(II) monoradical complex with a bis(salicylidene)- diamine ligand

Laurent Benisvy, Ramu Kannappan, Yu Fei Song, Sergey Milikisyants, Martina Huber, Ilpo Mutikainen, Urho Turpeinen, Patrick Gamez, Leonardo Bernasconi, Evert Jan Baerends, František Hartl, Jan Reedijk

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

44 Scopus citations

Abstract

The new square-planar Ni^II-N₂O₂ complex [Ni(^MeL)] (1^Me), where ^MeL stands for the dianionic phenolato form of N,N′-bis(3,5-di-tert-butyl-salicylidene)-4,5- dimethyl-1,2-phenylenediamine (^MeLH₂), has been synthesised and fully characterised. X-ray crystallography was also used for the characterisation. The electrochemical one-electron oxidation of 1^Me produces the thermally stable (within the temperature range 10-295 K) cationic species (1^Me)⁺. The UV/Vis and X-band EPR experimental data, supported by DFT calculations, indicate that (1^Me)⁺ is best described as a Ni^II monoradical complex and, thus, does NOT exist in a Ni^III ground state, in contrast to its demethylated counterpart [Ni(^HL)]⁺ (1^H)⁺ below 170 K.

Original language	English
Pages (from-to)	637-642
Number of pages	6
Journal	European Journal of Inorganic Chemistry
Issue number	5
DOIs	https://doi.org/10.1002/ejic.200601015
State	Published - 2007
Externally published	Yes

Keywords

Density functional calculations
EPR spectroscopy
Nickel(II) complexes
Phenoxyl radicals
Redox chemistry
Spectroelectrochemistry

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10.1002/ejic.200601015

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title = "A square-planar nickel(II) monoradical complex with a bis(salicylidene)- diamine ligand",

abstract = "The new square-planar NiII-N2O2 complex [Ni(MeL)] (1Me), where MeL stands for the dianionic phenolato form of N,N′-bis(3,5-di-tert-butyl-salicylidene)-4,5- dimethyl-1,2-phenylenediamine (MeLH2), has been synthesised and fully characterised. X-ray crystallography was also used for the characterisation. The electrochemical one-electron oxidation of 1Me produces the thermally stable (within the temperature range 10-295 K) cationic species (1Me)+. The UV/Vis and X-band EPR experimental data, supported by DFT calculations, indicate that (1Me)+ is best described as a NiII monoradical complex and, thus, does NOT exist in a NiIII ground state, in contrast to its demethylated counterpart [Ni(HL)]+ (1H)+ below 170 K.",

keywords = "Density functional calculations, EPR spectroscopy, Nickel(II) complexes, Phenoxyl radicals, Redox chemistry, Spectroelectrochemistry",

author = "Laurent Benisvy and Ramu Kannappan and Song, {Yu Fei} and Sergey Milikisyants and Martina Huber and Ilpo Mutikainen and Urho Turpeinen and Patrick Gamez and Leonardo Bernasconi and Baerends, {Evert Jan} and Franti{\v s}ek Hartl and Jan Reedijk",

year = "2007",

doi = "10.1002/ejic.200601015",

language = "אנגלית",

pages = "637--642",

journal = "European Journal of Inorganic Chemistry",

issn = "1434-1948",

publisher = "Wiley-VCH Verlag",

number = "5",

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T1 - A square-planar nickel(II) monoradical complex with a bis(salicylidene)- diamine ligand

AU - Benisvy, Laurent

AU - Kannappan, Ramu

AU - Song, Yu Fei

AU - Milikisyants, Sergey

AU - Huber, Martina

AU - Mutikainen, Ilpo

AU - Turpeinen, Urho

AU - Gamez, Patrick

AU - Bernasconi, Leonardo

AU - Baerends, Evert Jan

AU - Hartl, František

AU - Reedijk, Jan

PY - 2007

Y1 - 2007

N2 - The new square-planar NiII-N2O2 complex [Ni(MeL)] (1Me), where MeL stands for the dianionic phenolato form of N,N′-bis(3,5-di-tert-butyl-salicylidene)-4,5- dimethyl-1,2-phenylenediamine (MeLH2), has been synthesised and fully characterised. X-ray crystallography was also used for the characterisation. The electrochemical one-electron oxidation of 1Me produces the thermally stable (within the temperature range 10-295 K) cationic species (1Me)+. The UV/Vis and X-band EPR experimental data, supported by DFT calculations, indicate that (1Me)+ is best described as a NiII monoradical complex and, thus, does NOT exist in a NiIII ground state, in contrast to its demethylated counterpart [Ni(HL)]+ (1H)+ below 170 K.

AB - The new square-planar NiII-N2O2 complex [Ni(MeL)] (1Me), where MeL stands for the dianionic phenolato form of N,N′-bis(3,5-di-tert-butyl-salicylidene)-4,5- dimethyl-1,2-phenylenediamine (MeLH2), has been synthesised and fully characterised. X-ray crystallography was also used for the characterisation. The electrochemical one-electron oxidation of 1Me produces the thermally stable (within the temperature range 10-295 K) cationic species (1Me)+. The UV/Vis and X-band EPR experimental data, supported by DFT calculations, indicate that (1Me)+ is best described as a NiII monoradical complex and, thus, does NOT exist in a NiIII ground state, in contrast to its demethylated counterpart [Ni(HL)]+ (1H)+ below 170 K.

KW - Density functional calculations

KW - EPR spectroscopy

KW - Nickel(II) complexes

KW - Phenoxyl radicals

KW - Redox chemistry

KW - Spectroelectrochemistry

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DO - 10.1002/ejic.200601015

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SN - 1434-1948

SP - 637

EP - 642

JO - European Journal of Inorganic Chemistry

JF - European Journal of Inorganic Chemistry

IS - 5

ER -

A square-planar nickel(II) monoradical complex with a bis(salicylidene)- diamine ligand

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Keywords

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