An unusual Pd(iii) oxidation state in the Pd-Cl chain complex with high thermal stability and electrical conductivity

Mohammad Rasel Mian; Masanori Wakizaka; Takefumi Yoshida; Hiroaki Iguchi; Shinya Takaishi; Unjila Afrin; Tatsuya Miyamoto; Hiroshi Okamoto; Hisaaki Tanaka; Shin Ichi Kuroda; Brian K. Breedlove; Masahiro Yamashita

doi:10.1039/d0dt03848b

An unusual Pd(iii) oxidation state in the Pd-Cl chain complex with high thermal stability and electrical conductivity

Mohammad Rasel Mian, Masanori Wakizaka, Takefumi Yoshida, Hiroaki Iguchi, Shinya Takaishi, Unjila Afrin, Tatsuya Miyamoto, Hiroshi Okamoto, Hisaaki Tanaka, Shin Ichi Kuroda, Brian K. Breedlove, Masahiro Yamashita

SCI - Chemistry

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

8 Citations (Scopus)

Abstract

The Pd(iii) oxidation state is unusual and unstable since it strongly tends to disproportionate. We synthesized the quasi-one-dimensional (1D) halogen-bridged Pd(iii)-Cl complex [Pd(dabdOH)₂Cl]Cl₂(1-Cl; dabdOH = (2S,3S)-2,3-diaminobutane-1,4-diol) with multiple hydrogen bonds. From single-crystal X-ray diffraction, the bridging Cl⁻ions were located at the midpoint of the Pd-Cl-Pd moieties in the 1D chains, indicating that the Pd ions are in a Pd(iii) average valence (AV) state. Moreover, bright spots for the Pd(iii) d_z2orbitals in the upper Hubbard band above the Fermi level were observed every ∼5 Å using scanning tunnelling microscopy. These results clearly indicate that the Pd ions are in a Pd(iii) AV state in1-Cl. In addition,1-Clhas the highest thermal stability (470 K) among the Pd(iii) complexes reported and the highest electrical conductivity (0.6 S cm⁻¹at 300 K) among the 1D Pd-Cl chains reported so far.

Original language	English
Pages (from-to)	1614-1619
Number of pages	6
Journal	Dalton Transactions
Volume	50
Issue number	5
DOIs	https://doi.org/10.1039/d0dt03848b
Publication status	Published - 2021 Feb 7

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@article{94748945759249aaa0764e556e5cdbe2,

title = "An unusual Pd(iii) oxidation state in the Pd-Cl chain complex with high thermal stability and electrical conductivity",

abstract = "The Pd(iii) oxidation state is unusual and unstable since it strongly tends to disproportionate. We synthesized the quasi-one-dimensional (1D) halogen-bridged Pd(iii)-Cl complex [Pd(dabdOH)2Cl]Cl2(1-Cl; dabdOH = (2S,3S)-2,3-diaminobutane-1,4-diol) with multiple hydrogen bonds. From single-crystal X-ray diffraction, the bridging Cl−ions were located at the midpoint of the Pd-Cl-Pd moieties in the 1D chains, indicating that the Pd ions are in a Pd(iii) average valence (AV) state. Moreover, bright spots for the Pd(iii) dz2orbitals in the upper Hubbard band above the Fermi level were observed every ∼5 {\AA} using scanning tunnelling microscopy. These results clearly indicate that the Pd ions are in a Pd(iii) AV state in1-Cl. In addition,1-Clhas the highest thermal stability (470 K) among the Pd(iii) complexes reported and the highest electrical conductivity (0.6 S cm−1at 300 K) among the 1D Pd-Cl chains reported so far.",

author = "Mian, {Mohammad Rasel} and Masanori Wakizaka and Takefumi Yoshida and Hiroaki Iguchi and Shinya Takaishi and Unjila Afrin and Tatsuya Miyamoto and Hiroshi Okamoto and Hisaaki Tanaka and Kuroda, {Shin Ichi} and Breedlove, {Brian K.} and Masahiro Yamashita",

note = "Funding Information: This work was supported by JSPS KAKENHI Grant Numbers JP15K17828 (H. I.), JP18K14233 (H. I.), JP18H04498 (H. I.), JP18J13022 (M. R. M.), JP18H01166 (H. O.) and JP19H05631 (H. I., S. T. and M. Y.), by JST CREST Grant Number JPMJCR1661 (H. O.), by the Toyota Riken Scholar Program (H. I.) and by Kato Foundation for Promotion of Science KJ-2916 (H. I.), Japan. M. Y. thanks the 111 Project (B18030) from China for the support. Publisher Copyright: {\textcopyright} The Royal Society of Chemistry 2020.",

year = "2021",

month = feb,

day = "7",

doi = "10.1039/d0dt03848b",

language = "English",

volume = "50",

pages = "1614--1619",

journal = "Dalton Transactions",

issn = "1477-9226",

publisher = "Royal Society of Chemistry",

number = "5",

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TY - JOUR

T1 - An unusual Pd(iii) oxidation state in the Pd-Cl chain complex with high thermal stability and electrical conductivity

AU - Mian, Mohammad Rasel

AU - Wakizaka, Masanori

AU - Yoshida, Takefumi

AU - Iguchi, Hiroaki

AU - Takaishi, Shinya

AU - Afrin, Unjila

AU - Miyamoto, Tatsuya

AU - Okamoto, Hiroshi

AU - Tanaka, Hisaaki

AU - Kuroda, Shin Ichi

AU - Breedlove, Brian K.

AU - Yamashita, Masahiro

N1 - Funding Information: This work was supported by JSPS KAKENHI Grant Numbers JP15K17828 (H. I.), JP18K14233 (H. I.), JP18H04498 (H. I.), JP18J13022 (M. R. M.), JP18H01166 (H. O.) and JP19H05631 (H. I., S. T. and M. Y.), by JST CREST Grant Number JPMJCR1661 (H. O.), by the Toyota Riken Scholar Program (H. I.) and by Kato Foundation for Promotion of Science KJ-2916 (H. I.), Japan. M. Y. thanks the 111 Project (B18030) from China for the support. Publisher Copyright: © The Royal Society of Chemistry 2020.

PY - 2021/2/7

Y1 - 2021/2/7

N2 - The Pd(iii) oxidation state is unusual and unstable since it strongly tends to disproportionate. We synthesized the quasi-one-dimensional (1D) halogen-bridged Pd(iii)-Cl complex [Pd(dabdOH)2Cl]Cl2(1-Cl; dabdOH = (2S,3S)-2,3-diaminobutane-1,4-diol) with multiple hydrogen bonds. From single-crystal X-ray diffraction, the bridging Cl−ions were located at the midpoint of the Pd-Cl-Pd moieties in the 1D chains, indicating that the Pd ions are in a Pd(iii) average valence (AV) state. Moreover, bright spots for the Pd(iii) dz2orbitals in the upper Hubbard band above the Fermi level were observed every ∼5 Å using scanning tunnelling microscopy. These results clearly indicate that the Pd ions are in a Pd(iii) AV state in1-Cl. In addition,1-Clhas the highest thermal stability (470 K) among the Pd(iii) complexes reported and the highest electrical conductivity (0.6 S cm−1at 300 K) among the 1D Pd-Cl chains reported so far.

AB - The Pd(iii) oxidation state is unusual and unstable since it strongly tends to disproportionate. We synthesized the quasi-one-dimensional (1D) halogen-bridged Pd(iii)-Cl complex [Pd(dabdOH)2Cl]Cl2(1-Cl; dabdOH = (2S,3S)-2,3-diaminobutane-1,4-diol) with multiple hydrogen bonds. From single-crystal X-ray diffraction, the bridging Cl−ions were located at the midpoint of the Pd-Cl-Pd moieties in the 1D chains, indicating that the Pd ions are in a Pd(iii) average valence (AV) state. Moreover, bright spots for the Pd(iii) dz2orbitals in the upper Hubbard band above the Fermi level were observed every ∼5 Å using scanning tunnelling microscopy. These results clearly indicate that the Pd ions are in a Pd(iii) AV state in1-Cl. In addition,1-Clhas the highest thermal stability (470 K) among the Pd(iii) complexes reported and the highest electrical conductivity (0.6 S cm−1at 300 K) among the 1D Pd-Cl chains reported so far.

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UR - http://www.scopus.com/inward/citedby.url?scp=85100814934&partnerID=8YFLogxK

U2 - 10.1039/d0dt03848b

DO - 10.1039/d0dt03848b

M3 - Article

C2 - 33332512

AN - SCOPUS:85100814934

SN - 1477-9226

VL - 50

SP - 1614

EP - 1619

JO - Dalton Transactions

JF - Dalton Transactions

IS - 5

ER -

An unusual Pd(iii) oxidation state in the Pd-Cl chain complex with high thermal stability and electrical conductivity

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