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An Unusual Example of Hypervalent Silicon: A Five‐Coordinate Silyl Group Bridging Two Palladium or Nickel Centers through a Nonsymmetrical Four‐Center Two‐Electron Bond
Author(s) -
Nova Ainara,
Suh HeeWon,
Schmeier Timothy J.,
Guard Louise M.,
Eisenstein Odile,
Hazari Nilay,
Maseras Feliu
Publication year - 2014
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.201307618
Subject(s) - hypervalent molecule , chemistry , crystallography , palladium , nickel , center (category theory) , silicon , natural bond orbital , density functional theory , computational chemistry , biochemistry , organic chemistry , reagent , catalysis
Pd and Ni dimers supported by PSiP ligands in which two hypervalent five‐coordinate Si atoms bridge the two metal centers are reported. Crystallographic characterization revealed a rare square‐pyramidal geometry at Si and an unusual asymmetric M 2 Si 2 core (M=Pd or Ni). DFT calculations showed that the unusual structure of the core is also found in a model in which the phosphine and Si centers are not part of a pincer group, thus indicating that the observed geometry is not imposed by the PSiP ligand. NBO analysis showed that an asymmetric four‐center two‐electron (4c‐2e) bond stabilizes the hypervalent Si atoms in the M 2 Si 2 core.