Synthese von [LRe(CO)<sub />3]⁺-Komplexen mit makrocyclischen Liganden Die Kristallstrukturen von 1,4,7-Triazacyclononan-tricarbonylrhenium( I)-thiocyanat und 1,4,7-Trithiacyclononan-tricarbonylrhenium( I) -bromid-hemihydrat / Synthesis of [LRe(CO)₃]⁺ Complexes with Macrocyclic Ligands The Crystal Structures of 1,4,7-Triazacyclononane-tricarbonyl-rhenium(I) Thiocyanate and of 1,4,7-Trithiacyclononane-tricarbonyl-rhenium(I) Bromide Hemihydrate

Abstract

The tridentate macrocyclic ligands 1,4,7-triazacyclononane, its thia analogue 1,4,7-trithiacyclononane, 1-oxa-4,7-diazacyclononane, and N,N′,N″-trimethyl-1 ,4,7-triazacyclononane react with Re(CO) 5 Br in dimethylformamide to yield colorless, air-stable [LRe(CO) 3 ]Br complexes (L = tridentate macrocycle). With Mn(CO) 5 Br only the cyclic amines react to afford yellow-orange [LMn(CO) 3 ]Br complexes whereas 1,4,7-trithiacyclononane does not give stable complexes of manganese. The crystal structures of [([9]aneN 3 )Re(CO) 3 ](NCS) and [([9]aneS 3 )Re(CO) 3 ]Br · 1/2 H 2 O have been determined. The former crystallizes in the orthorhombic space group P bca (a = 12/763(4), b = 12.662(5), c = 17.472(9) Å; Z = 8); whereas the latter crystallizes in the monoclinic space group P2 1 /c (a = 9.444(1). b = 11.797(2), c = 28.095(3) Å. β = 90,86(1); Z = 8).