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Synthesis and Properties of Cryptands with a Thioether Bridge and π‐Donors – Silver( I ) and Copper( I )‐Complexes
Author(s) -
Koschabek René,
Gleiter Rolf,
Rominger Frank
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.200500685
Subject(s) - chemistry , trifluoromethanesulfonate , chalcogen , thioether , copper , metal , cryptand , nitrogen atom , polymer chemistry , bicyclic molecule , nitrogen , stereochemistry , crystallography , ion , organic chemistry , ring (chemistry) , catalysis
Abstract The syntheses of seven bridgehead diazabicycloalkanes are reported. The bridges are represented by either a thioether chain and two 3‐hexyne units ( 4 and 6 – 8 ), one selenoether chain and two 3‐hexyne units ( 5 ), or one dithioether chain and two 4,4′‐diethylbiphenyl units ( 9 , 10 ). X‐ray investigations reveal for 4 – 10 the in / in conformation at the bridgehead nitrogen atoms. Reactions with Cu I triflate yield the endohedral Cu I complexes of 4 – 6 . Endohedral complexes of 6 , 7 , and 10 were isolated with silver triflate. X‐ray investigations and spectroscopic studies on the metal complexes reveal interactions between the metal ion and the nitrogen‐, chalcogen‐, and π‐units. In addition to the bicyclic systems 4 – 10 we synthesized the tripodal systems 28 – 33 in a one‐pot reaction. In the cases of 28 and 33 we were able to isolate the corresponding Ag I complexes. X‐ray studies show an interaction between the metal ion and the nitrogen atom and one double bond of each of the three adjacent phenyl rings. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006)