In:
European Journal of Inorganic Chemistry, Wiley, Vol. 2007, No. 1 ( 2007-01), p. 90-102
Abstract:
The effect of N ‐alkylation on the ligating properties of the Robson‐type 24‐membered hexaazadithiophenolate macrocycle H 2 L 1 [13,27‐bis( tert ‐butyl)‐3,6,9,17,20,23‐hexaazatricyclo[23.3.1 11,15 ]triaconta‐1(28),11,13,15(30),25,26‐hexaene‐29,30‐dithiol] has been examined. Two new derivatives (H 2 L 3 and H 2 L 4 ) of H 2 L 1 have been prepared. H 2 L 3 is a dimethylated derivative of H 2 L 1 and H 2 L 4 is a tetraethylated derivative of H 2 L 3 . A series of complexes of the type [(L R )M II 2 (μ‐Cl)] + [R = 1, M = Cd ( 10 ), R = 3, M = Ni ( 8 ), M = Cd ( 12 ), R = 4, M = Ni ( 9 ), M = Cd ( 13 )] have been prepared and structurally characterised. The X‐ray crystal structure determination of these dioctahedral complexes with an N 3 M(S) 2 (μ‐Cl)MN 3 core structure has revealed two conformations of the supporting ligands. In 8 , 9 , 10 and 12 the ligands adopt a folded C s ‐symmetric conformation of type A whereas in the cadmium complex 13 the alternative C 2v ‐symmetric “bowl‐shaped” conformation (type B) is present. A structural comparison has allowed us to determine the factors that determine the ligand conformations. It has been established that the ligand conformations adopted depend not only on the co‐ligand but also on the metal ion radius and the N ‐alkylation grade. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007)
Type of Medium:
Online Resource
ISSN:
1434-1948
,
1099-0682
DOI:
10.1002/ejic.v2007:1
DOI:
10.1002/ejic.200600318
Language:
English
Publisher:
Wiley
Publication Date:
2007
detail.hit.zdb_id:
1475009-0
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