Structures of bis(1-thia-4,7-diazacyclononane)copper(II) nitrate and bis(1,7-diaza-4-thiaheptane)copper(II) nitrate. A different conformation for the coordinated macrocycle

Abstract

Die beiden Titelkomplexe (I) und (II) werden durch Umsetzung von Cu(II)‐nitrattrihydrat mit den entsprechenden Liganden in Ethanol bzw. Methanol synthetisiert und durch Röntgenstrukturanalysen [(1): RG Pbca, Z=4; (II): RG PI, Z=2] sowie Elektronenspektren charakterisiert.

Structures of the cis and trans isomers of the bis(1-thia-4,7-diazacyclononane)cobalt(III) cation

“…In all complexes of the related ligand tacn (l,4,7-triazacyclononane), the conformation with all rings having the same chirality (222 or ~6b') is present, and this arrangement has also been found in I Ni(tasn)21(NO3) 2 (Hart, Boeyens, Michael & Hancock, 1983). The conformation found here has been observed previously in the structure of ICu(tasn)21(NO3) 2 (Boeyens, Dobson & Hancock, 1985). In that report it was suggested that the mixed-chirality conformation was stabilized by the longer metal-to-donor-atom bond lengths of the copper complex compared to the nickel complex.…”

“…Two geometric isomers are possible for octahedral IM(tasn)21 -'~ complexes, designated cis and trans according to the arrangement of the S atoms about the metal. Structures of both [Cu(tasn)El(NO3) 2 and [Ni(tasn)El(NO3) 2 have revealed the trans isomer (Boeyens, Dobson & Hancock, 1985;Hart, Boeyens, Michael & Hancock, 1983). Preparation of the Co I~ complex was first described by Gahan, Lawrance & Sargeson (1982) and they and Nonoyama & Ishida (1984) obtained spectroscopic evidence for the existence of more than one isomer.…”

Crystal and solution structure of a pendant-armed macrocyclic complex of palladium(II)

“…The formation of the dihydrobromide salt of 1,4-diaza-7-thiacyclononane (11) was achieved by literature procedures (10,11) and proceeds with reasonable yields. Care must be taken during the detosylation of the amines to avoid cleavage of the C-S bonds with the ring.…”

Transition metal complexes of ligands containing 3,5-dimethylpyrazolyl groups and thioether functions. The crystal and molecular structure of (1,12-bis(3,5-dimethylpyrazol-1-yl)-2,11-diaza-5,8-dithiadodecane)nickel(II)-bis(tetrafluoroborate)

“…Besides biochemical relevance, sulfur-containing chelates with firs-row transition metals are also of more general coordination chemistry interest _ The soft character of the sulfur ligand allows investigations concerning the influence upon electronic spectroscopy [ll, 15-171, the stabilization of low valent oxidation states , the stereochemical properties [15][16][17]211 and even the potential application in homogeneous catalysis [ 191. With this purpose the ligands 1,12-bis(3,5di-methylpyrazol-1 -yl)-2,ll diaza_5,8dithiadodecane, abbreviated dsbd, and l,l,lO,lO-tetrakis(3,5di-methylpyrazol-l-ylmethyl)-l,1Odiaza-4,7dithiadecane, abbreviated dstd, were synthesized and their coordination chemistry towards first-row transition metals was investigated. The dsbd ligand combines two thioether sulfur atoms, two secondary amines and two pyrazole rings in a conformation which would allow chelation to one metal ion, thus yielding a potentially hexadentate ligand.…”