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

Research output: Contribution to journalArticlepeer-review

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 Clions 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.

Original languageEnglish
Pages (from-to)1614-1619
Number of pages6
JournalDalton Transactions
Volume50
Issue number5
DOIs
Publication statusPublished - 2021 Feb 7

ASJC Scopus subject areas

  • Inorganic Chemistry

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