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Triple‐decker tin and lead cations
Author(s) -
Cowley Alan H.,
Jones Jamie N.,
Macdonald Charles L. B.
Publication year - 2005
Publication title -
applied organometallic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.53
H-Index - 71
eISSN - 1099-0739
pISSN - 0268-2605
DOI - 10.1002/aoc.827
Subject(s) - chemistry , toluene , cationic polymerization , crystallography , molecule , tin , indium , dissociation (chemistry) , density functional theory , stereochemistry , medicinal chemistry , computational chemistry , organic chemistry
The triple‐decker cation salts [(η 5 ‐C 5 Me 5 )M(µ‐η 5 ‐C 5 Me 5 )M(η 5 ‐C 5 Me 5 )][B(C 6 F 5 ) 4 ] (M = Sn, Pb) have been prepared by treatment of [(η 5 ‐C 5 Me 5 )M][B(C 6 F 5 ) 4 ] with the corresponding metallocenes, [M(η 5 ‐C 5 Me 5 ) 2 ] (M = Sn, Pb). Investigation of the structures of these triple‐decker systems by X‐ray crystallography revealed an overall cis‐type cationic geometry. In solution, NMR studies indicate that the triple‐decker cations undergo rapid, reversible dissociation. The reaction of [In(η 5 ‐C 5 Me 5 )] with an equimolar quantity of H 2 O·B(C 6 F 5 ) 3 and B(C 6 F 5 ) 3 ] afforded [(η 6 ‐toluene)In(µ‐η 5 ‐C 5 Me 5 )In(η 6 ‐toluene)][(C 6 F 5 ) 3 B(OH)B(C 6 F 5 ) 3 ]. Density functional theory calculations on a model system indicate that the capping toluene molecules in this di‐indium cation are weakly bonded. Use of the smaller counter‐ion [B(C 6 F 5 ) 4 ] − results in isolation of the inverse sandwich cation [In(µ‐η 5 ‐C 5 Me 5 )In] + . Copyright © 2005 John Wiley & Sons, Ltd.