A Square-Planar Complex of Platinum(0)

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 dist...

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Bibliographic Details
Published in:Angewandte Chemie International Edition 2016-12, Vol.55 (49), p.15347-15350
Main Authors: Takeuchi, Katsuhiko, Taguchi, Hiro-omi, Tanigawa, Ippei, Tsujimoto, Shota, Matsuo, Tsukasa, Tanaka, Hiromasa, Yoshizawa, Kazunari, Ozawa, Fumiyuki
Format: Article
Language:English
Subjects:
Geometry
phosphaalkene ligands
pincer complexes
platinum
relativistic effects
square-planar complexes
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Summary: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. Unusual coordination geometry: A platinum(0) complex with a PNP‐pincer‐type phosphaalkene ligand adopts a highly planar geometry around platinum, which is very uncommon for formal d10 complexes. DFT calculations indicate that the planar structure is tightly linked with strong s–d hybridization due to relativistic effects.
ISSN:1433-7851
1521-3773
DOI:10.1002/anie.201609515