Stabilization of Pd(iii) states in nano-wire coordination complexes

Masahiro Yamashita; Shinya Takaishi

doi:10.1039/c002097d

Stabilization of Pd(iii) states in nano-wire coordination complexes

Masahiro Yamashita, Shinya Takaishi

Research output: Contribution to journal › Review article

21 Citations (Scopus)

Abstract

In spite of a long history of quasi-one-dimensional halogen-bridged complexes (MX-chains), all Pt and Pd complexes form the charge-density wave (CDW) state (-X⋯M^II⋯X-M^IV-X⋯), while all Ni complexes form Mott-Hubbard (MH) states (-X-Ni^III-X-Ni ^III-X-), without exception. We have succeeded in stabilizing the Pd(iii) MH state for the first time by utilizing the following two methods: partial substitution with Ni(iii) ions, [Ni_1-xPd_x(chxn) ₂Br]Br₂, and chemical pressure via long alkyl chains introduced as counter-anions, [Pd(en)₂Br](C_n-Y) ₂·H₂O. In both systems, it has been revealed that the electronic state of bromo-bridged Pd compounds are determined by the Pd⋯Pd distances, in other words, CDW and MH states are stabilized when Pd⋯Pd distances are longer and shorter than 5.26 Å, respectively.

Original language	English
Pages (from-to)	4438-4448
Number of pages	11
Journal	Chemical Communications
Volume	46
Issue number	25
DOIs	https://doi.org/10.1039/c002097d
Publication status	Published - 2010 Jul 7

ASJC Scopus subject areas

Catalysis
Electronic, Optical and Magnetic Materials
Ceramics and Composites
Chemistry(all)
Surfaces, Coatings and Films
Metals and Alloys
Materials Chemistry

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Yamashita, M., & Takaishi, S. (2010). Stabilization of Pd(iii) states in nano-wire coordination complexes. Chemical Communications, 46(25), 4438-4448. https://doi.org/10.1039/c002097d

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title = "Stabilization of Pd(iii) states in nano-wire coordination complexes",

abstract = "In spite of a long history of quasi-one-dimensional halogen-bridged complexes (MX-chains), all Pt and Pd complexes form the charge-density wave (CDW) state (-X⋯MII⋯X-MIV-X⋯), while all Ni complexes form Mott-Hubbard (MH) states (-X-NiIII-X-Ni III-X-), without exception. We have succeeded in stabilizing the Pd(iii) MH state for the first time by utilizing the following two methods: partial substitution with Ni(iii) ions, [Ni1-xPdx(chxn) 2Br]Br2, and chemical pressure via long alkyl chains introduced as counter-anions, [Pd(en)2Br](Cn-Y) 2·H2O. In both systems, it has been revealed that the electronic state of bromo-bridged Pd compounds are determined by the Pd⋯Pd distances, in other words, CDW and MH states are stabilized when Pd⋯Pd distances are longer and shorter than 5.26 {\AA}, respectively.",

author = "Masahiro Yamashita and Shinya Takaishi",

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AU - Yamashita, Masahiro

AU - Takaishi, Shinya

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N2 - In spite of a long history of quasi-one-dimensional halogen-bridged complexes (MX-chains), all Pt and Pd complexes form the charge-density wave (CDW) state (-X⋯MII⋯X-MIV-X⋯), while all Ni complexes form Mott-Hubbard (MH) states (-X-NiIII-X-Ni III-X-), without exception. We have succeeded in stabilizing the Pd(iii) MH state for the first time by utilizing the following two methods: partial substitution with Ni(iii) ions, [Ni1-xPdx(chxn) 2Br]Br2, and chemical pressure via long alkyl chains introduced as counter-anions, [Pd(en)2Br](Cn-Y) 2·H2O. In both systems, it has been revealed that the electronic state of bromo-bridged Pd compounds are determined by the Pd⋯Pd distances, in other words, CDW and MH states are stabilized when Pd⋯Pd distances are longer and shorter than 5.26 Å, respectively.

AB - In spite of a long history of quasi-one-dimensional halogen-bridged complexes (MX-chains), all Pt and Pd complexes form the charge-density wave (CDW) state (-X⋯MII⋯X-MIV-X⋯), while all Ni complexes form Mott-Hubbard (MH) states (-X-NiIII-X-Ni III-X-), without exception. We have succeeded in stabilizing the Pd(iii) MH state for the first time by utilizing the following two methods: partial substitution with Ni(iii) ions, [Ni1-xPdx(chxn) 2Br]Br2, and chemical pressure via long alkyl chains introduced as counter-anions, [Pd(en)2Br](Cn-Y) 2·H2O. In both systems, it has been revealed that the electronic state of bromo-bridged Pd compounds are determined by the Pd⋯Pd distances, in other words, CDW and MH states are stabilized when Pd⋯Pd distances are longer and shorter than 5.26 Å, respectively.

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