A Square-Planar Complex of Platinum(0)

Katsuhiko Takeuchi, Hiro Omi Taguchi, Ippei Tanigawa, Shota Tsujimoto, Tsukasa Matsuo, Hiromasa Tanaka, Kazunari Yoshizawa, Fumiyuki Ozawa

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Abstract

The Pt0complex [Pt(PPh3)(Eind2-BPEP)] with a pyridine-based PNP-pincer-type phosphaalkene ligand (Eind2-BPEP) has a highly planar geometry around Pt with ∑(Pt)=358.6°. This coordination geometry is very uncommon for formal d10complexes, and the Pd and Ni homologues with the same ligands adopt distorted tetrahedral geometries. DFT calculations reveal that both the Pt and Pd complexes are M0species with nearly ten valence electrons on the metals whereas their atomic orbital occupancies are evidently different from one another. The Pt complex has a higher occupancy of the atomic 6s orbital because of strong s–d hybridization due to relativistic effects, thereby adopting a highly planar geometry reflecting the shape and orientation of the partially unoccupied dx2y2orbital.

Original languageEnglish
Pages (from-to)15347-15350
Number of pages4
JournalAngewandte Chemie - International Edition
Volume55
Issue number49
DOIs
Publication statusPublished - Jan 1 2016

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All Science Journal Classification (ASJC) codes

  • Catalysis
  • Chemistry(all)

Cite this

Takeuchi, K., Taguchi, H. O., Tanigawa, I., Tsujimoto, S., Matsuo, T., Tanaka, H., ... Ozawa, F. (2016). A Square-Planar Complex of Platinum(0). Angewandte Chemie - International Edition, 55(49), 15347-15350. https://doi.org/10.1002/anie.201609515