Premium
Theoretical Study of Pd 11 Si 6 Nanosheet Compounds Including Seven‐Coordinated Si Species and Its Ge Analogues
Author(s) -
Chen Yue,
Sunada Yusuke,
Nagashima Hideo,
Sakaki Shigeyoshi
Publication year - 2016
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201503489
Subject(s) - crystallography , nanosheet , atom (system on chip) , pentagonal bipyramidal molecular geometry , atomic orbital , chemistry , density functional theory , bipyramid , silicon , materials science , electron , crystal structure , nanotechnology , computational chemistry , physics , organic chemistry , quantum mechanics , computer science , embedded system
Nanosheet compounds Pd 11 (Si i Pr) 2 (Si i Pr 2 ) 4 (CN t Bu) 10 ( 1 ) and Pd 11 (Si i Pr) 2 (Si i Pr 2 ) 4 (CNMes) 10 ( 2 ), containing two Pd 7 (Si i Pr)(Si i Pr 2 ) 2 (CNR) 4 plates (R= t Bu or Mes) connected with three common Pd atoms, were investigated with DFT method. All Pd atoms are somewhat positively charged and the electron density is accumulated between the Pd and Si atoms, indicating that a charge transfer (CT) occurs from the Pd to the Si atoms of the SiMe 2 and SiMe groups. Negative regions of the Laplacian of the electron density were found between the Pd and Si atoms. A model of a seven‐coordinated Si species, that is, Pd 5 (Pd−SiMe), is predicted to be a stable pentagonal bipyramidal molecule. Five Pd atoms in the equatorial plane form bonding overlaps with two 3p orbitals of the Si atom. This is a new type of hypervalency. The Ge analogues have geometry and an electronic structure similar to those of the Si compounds. But their formation energies are smaller than those of the Si analogues. The use of the element Si is crucial to synthesize these nanoplate compounds.