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Pentacoordination at Germanium by Transannular Bonding of Sulfur or Oxygen in an Eight‐Membered Ring: An Experimental and Theoretical Study
Author(s) -
GonzálezMontiel Simplicio,
AndradeLópez Noemí,
GarcíaMontalvo Verónica,
Cogordan Juan Antonio,
AlvaradoRodríguez José G.
Publication year - 2006
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/ejic.200600424
Subject(s) - chemistry , chalcogen , natural bond orbital , intramolecular force , crystallography , germanium , ring (chemistry) , halogen , trigonal bipyramidal molecular geometry , bromide , atom (system on chip) , stereochemistry , computational chemistry , inorganic chemistry , density functional theory , silicon , crystal structure , organic chemistry , alkyl , computer science , embedded system
Abstract Treatment of L n GeCl 4– n with D(C 6 H 4 SH) 2 in the presence of n BuLi leads to the formation of the stable compounds D(C 6 H 4 S) 2 GeL 1 L 2 (for D = S, L 1 = Cl, L 2 = Ph, 1 and L 1 = L 2 = Ph, 3 ; for D = O, L 1 = Cl, L 2 = Et, 4 and L 1 = L 2 = Ph, 5 ). The S(C 6 H 4 S) 2 Ge(Ph)Br compound ( 2 ) has been synthesised by halogen exchange from 1 and potassium bromide. X‐ray structure determinations of complexes 1 – 5 reveal that the germanium atom acts as an acceptor atom displaying an intramolecular transannular interaction with the chalcogen D atom. The geometry of the pentacoordinate Ge atom in the title compounds is described as distorted trigonal bipyramidal with a 64–31 % distortion displacement. The D→Ge (D = S, O) hypercoordinate interaction was studied by DFT methods using correlation consistent basis sets and relativistic ECP for Ge. NBO analysis showed that this interaction can be explained in terms of the interplay of covalent and Coulombic interactions. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006)