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Intramolecular Metal⋅⋅⋅π‐Arene Interactions in Neutral and Cationic Main Group Compounds
Author(s) -
Schwamm Ryan J.,
Fitchett Christopher M.,
Coles Martyn P.
Publication year - 2019
Publication title -
chemistry – an asian journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.18
H-Index - 106
eISSN - 1861-471X
pISSN - 1861-4728
DOI - 10.1002/asia.201801729
Subject(s) - chemistry , medicinal chemistry , amide , intramolecular force , substituent , ligand (biochemistry) , electrophile , cationic polymerization , synthon , salt (chemistry) , metal , adduct , main group element , inorganic chemistry , polymer chemistry , stereochemistry , transition metal , organic chemistry , biochemistry , receptor , catalysis
The role of intramolecular metal⋅⋅⋅π‐arene interactions has been investigated in the solid‐state structures of a series of main group compounds supported by the bulky amide ligands, [N( t Bu Ar ≠ )(SiR 3 )] − ( t Bu Ar ≠ =2,6‐(CHPh 2 ) 2 ‐4‐ t BuC 6 H 2 , R=Me, Ph). The lithium and potassium amide salts showed different patterns of solvation and demonstrated that the Si Ph 3 substituent is able to be involved in stabilizing the electrophilic metal. These group 1 metal compounds served as ligand transfer reagents to access a series of bismuth(III) halides. Chloride extraction from Bi(N{ t Bu Ar ≠ }{SiPh 3 })Cl 2 using AlCl 3 afforded the 1:1 salt [Bi(N{ t Bu Ar ≠ }{SiPh 3 })Cl][AlCl 4 ]. This was accompanied by a significant rearrangement of the stabilizing π‐arene contacts in the solid‐state. Attempted preparation of the corresponding tetraphenylborate salt resulted in phenyl‐transfer and generation of the neutral Bi(N{ t Bu Ar ≠ }{SiPh 3 })(Ph)Cl.