Synthesis and Properties of Cryptands with a Thioether Bridge and π-Donors – Silver(I) and Copper(I)-Complexes

✍ Scribed by René Koschabek; Rolf Gleiter; Frank Rominger

• Publisher: John Wiley and Sons
• Year: 2006
• Tongue: English
• Weight: 247 KB
• Volume: 2006
• Category: Article
• ISSN: 1434-1948
• DOI: 10.1002/ejic.200500685

✦ Synopsis

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)