Issue 5, 2021

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) dz2 orbitals 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 in 1-Cl. In addition, 1-Cl has the highest thermal stability (470 K) among the Pd(III) complexes reported and the highest electrical conductivity (0.6 S cm−1 at 300 K) among the 1D Pd–Cl chains reported so far.

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

Supplementary files

Article information

Article type
Paper
Submitted
09 nov 2020
Accepted
03 dec 2020
First published
09 dec 2020

Dalton Trans., 2021,50, 1614-1619

Author version available

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

M. R. Mian, M. Wakizaka, T. Yoshida, H. Iguchi, S. Takaishi, U. Afrin, T. Miyamoto, H. Okamoto, H. Tanaka, S. Kuroda, B. K. Breedlove and M. Yamashita, Dalton Trans., 2021, 50, 1614 DOI: 10.1039/D0DT03848B

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