Polyazamacrocycles. V. Structure of Isomeric 3,5,7,7,10,12,14,14-Octamethyl-1,4,8,11-tetraazacyclotetradecanes

Abstract

Reduction of 3,5,7,7,10,12,14,14-octamethyl-1,4,8,11-tetraazacyclotetradeca-4,11-diene (Me8[14]diene) with sodium borohydride yields three diastereomeric Me8[14]anes. These diastereomers can be separated through fractional crystallization from xylene. The structure of these isomers has been established on the bseis of their NMR spectra. The structure of one isomer has been confirmed by X-ray crystallography.

Two solvatomorphic forms of a copper complex formulated as Cu(L1)(ClO4)2·1.2H2O and Cu(L1)(ClO4)2, whereL1is 3,10-C-meso-3,5,7,7,10,12,14,14-octamethyl-1,4,8,11-tetraazacyclotetradecane

“…For the synthesis of L, reduction of 3,10-C-meso-Me 8 [14]diene dihydroperchlorate (Curtis et al, 1969) and resolution of isomeric Me 8 [14]anes were carried out as described in the literature (Bembi et al, 1989); ligand L in the present work corresponds to Lb in the latter cited paper. Regarding chirality, in the diene ligand there were originally two chiral centres and the reduction process gives rise to two further chiral centres.…”

cis-(Nitrato-κ2O,O′)(2,5,5,7,9,12,12,14-octamethyl-1,4,8,11-tetraazacyclotetradecane-κ4N,N′,N′′,N′′′)cadmium nitrate hemihydrate

“…For the crystal structure of the anhydrous form of the title complex, see: Hazari et al (2010). For the synthesis of the macrocyclic ligand, see: Bembi et al (1989).…”

“…The macrocyclic ligand, 3,10-C-meso-2, 5,5,7,9,12,12,14-octamethyl-1,4,8,11-tetraazacyclotetradecane (0.312 g, 1.0 mmol), prepared in accord with the literature procedure (Bembi et al, 1989), was dissolved in methanol (20 ml) in a round bottomed flask. Cadmium(II) nitrate hexahydrate (0.344 g, 1.0 mmol) in methanol (20 ml) was added drop wise to the round bottom flask with continuous stirring The mixture was heated for about 30 min.…”

Syntheses, characterization and anti‐microbial activities of palladium(II) and palladium(IV) complexes of 3,10‐C‐meso‐Me8[14]diene (L1) and its reduced isomeric anes (LA, LB and LC). Crystal and molecular structure of [PdL1][Pd(SCN)4]

“…2HClO 4 , [23] isolation of free diene, [15] L 1 , and reduction of this diene and separation of the isomeric Me 8 [14]anes to produce L A , L B and L C were performed according to literature methods. [24,25] L 1 (0.308 g, 1.0 mmol) and palladium(II) chloride (0.354 g, 2.0 mmol)) were dissolved separately in hot methylcyanide (150 ml). The ligand solution was added dropwise to metal solution while hot.…”

“…On the basis of MS, [15,24] 1 H-and 13 C{ 1 H}-NMR spectra [15,23,25] and X-ray crystallography, [25] the structures of L 1 , L A L B and L C were established as indicated in Fig. 1.…”