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A Square‐Planar Complex of Platinum(0)
Author(s) -
Takeuchi Katsuhiko,
Taguchi Hiroomi,
Tanigawa Ippei,
Tsujimoto Shota,
Matsuo Tsukasa,
Tanaka Hiromasa,
Yoshizawa Kazunari,
Ozawa Fumiyuki
Publication year - 2016
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.201609515
Subject(s) - planar , chemistry , crystallography , coordination geometry , platinum , tetrahedron , atom (system on chip) , tetrahedral molecular geometry , valence (chemistry) , valence electron , non bonding orbital , pincer movement , molecular orbital , geometry , electron , molecule , physics , crystal structure , catalysis , hydrogen bond , biochemistry , computer graphics (images) , organic chemistry , mathematics , quantum mechanics , computer science , embedded system
The Pt 0 complex [Pt(PPh 3 )(Eind 2 ‐BPEP)] with a pyridine‐based PNP‐pincer‐type phosphaalkene ligand (Eind 2 ‐BPEP) has a highly planar geometry around Pt with ∑(Pt)=358.6°. This coordination geometry is very uncommon for formal d 10 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 M 0 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 d x 2 - y 2orbital.
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