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.
Angew Chem Int Ed Engl
; 53(4): 1103-8, 2014 Jan 20.
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| ID: mdl-24338980
ABSTRACT
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 M2 Si2 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 M2 Si2 core.
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2014
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Article