A Square-Planar Complex of Platinum(0)

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

doi:10.1002/anie.201609515

A Square-Planar Complex of Platinum(0)

Angew Chem Int Ed Engl. 2016 Dec 5;55(49):15347-15350. doi: 10.1002/anie.201609515. Epub 2016 Nov 9.

Authors

Katsuhiko Takeuchi¹, Hiro-Omi Taguchi¹, Ippei Tanigawa¹, Shota Tsujimoto², Tsukasa Matsuo², Hiromasa Tanaka³, Kazunari Yoshizawa³, Fumiyuki Ozawa¹

Affiliations

¹ International Research Center for Elements Science (IRCELS), Institute for Chemical Research & IRCCS, Kyoto University, Uji, Kyoto, 611-0011, Japan.
² Department of Applied Chemistry, Faculty of Science and Engineering, Kindai University, Higashi-Osaka, Osaka, 577-8502, Japan.
³ Institute for Materials Chemistry and Engineering, International Research Center for Molecular Systems & IRCCS, Kyushu University, Nishi-ku, Fukuoka, 819-0395, Japan.

PMID: 27860032
DOI: 10.1002/anie.201609515

Abstract

The Pt⁰ complex [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 d¹⁰ complexes, 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 M⁰ species 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 dx2-y2 orbital.

Keywords: phosphaalkene ligands; pincer complexes; platinum; relativistic effects; square-planar complexes.

Publication types

Research Support, Non-U.S. Gov't