Pressure-induced metal-to-ligand electron transfer and the electrical conductivity of some Pt(II)-glyoximes.

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概要

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• Mid-infrared (900–1600 cm<SUP>−1</SUP>), visible absorption spectra and electrical resistance of bis(benzil dioximato)platinum(II) [abbreviated as Pt(bz)<SUB>2</SUB>], bis(dimethylglyoximato)platinum(II) [Pt(dmg)<SUB>2</SUB>], bis(1,2-cyclohexanedione dioximato)platinum(II) [Pt(cd)<SUB>2</SUB>], and bis(pyruvaldehyde dioximato)platinum(II) [Pt(pa)<SUB>2</SUB>] have been measured at high pressures. A decrease of the C=N frequency by −40.0 cm<SUP>−1</SUP>, with reduction of the dπ→π<SUP>*</SUP> optical transition intensity by \simeq14%, show that [Pt(bz)<SUB>2</SUB>] enhances thermally its dπ→π<SUP>*</SUP> electron transfer at high pressures up to 35 kbar. No such changes are observed for [Pt(dmg)<SUB>2</SUB>], [Pt(cd)<SUB>2</SUB>], and [Pt(pa)<SUB>2</SUB>]. This backbonding causes [Pt(bz)<SUB>2</SUB>] to release the instability, due to increasing overlapping of the electron clouds around Pt(II) at high pressures, that is the cause of the resistance minimum.

• 公益社団法人 日本化学会の論文

著者

• Nicol Malcolm

  Department of Chemistry, University of California, Los Angeles

• Hara Yoji

  Department of Chemistry, University of California, Los Angeles

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