Yves Boland

New mononuclear Cu(II) complexes and 1D chains with 4-Amino-4H-1,2,4-triazole

The crystal structures of two mononuclear Cu(II) NH2trz complexes [Cu(NH2trz)4(H2O)](AsF6)2 (I) and [Cu(NH2trz)4(H2O)](PF6)2 (II) as well as two coordination polymers [Cu(μ2-NH2trz)2Cl]Cl·H2O (III) and [Cu(μ2-NH2trz)2Cl] (SiF6)0.5·1.5H2O (IV) are presented. Cationic 1D chains with bridging bis-monodentate μ2-coordinated NH2trz and bridging μ2-coordinated chloride ligands are present in III and IV. In these coordination polymers, the Cu(II) ions are strongly antiferromagnetically coupled with J = −128.4 cm−1 for III and J = −143 cm−1 for IV (H = −J∑SiSi+1), due to the nature of the bridges between spin centers. Inter-chain interactions present in the crystal structures were taken into consideration, as well as g factors, which were determined experimentally, for the quantitative modeling of their magnetic properties.

Routes to novel mono- and bis-tetrazole compounds: synthesis, spectroscopic and structural characterization

Relatively easy-to-run synthetic routes to new mono- [1-(2-(4,5-dihydro-1H-imidazol-1-yl)ethyl)-1H-tetrazole (1) and 3-(2-(1H-tetrazol-1-yl)ethyl)oxazolidin-2-one (13)], and bis-tetrazole [N,N-bis(2-(1H-tetrazol-1-yl)ethyl)formamide (2), bis(2-(1H-tetrazol-1-yl)ethyl)amine (3), N-(2-(1H-tetrazol-1-yl)ethyl)-N-(2-(2-(1H-tetrazol-1-yl)ethylamino)ethyl)formamide (5), N1,N2-bis(2-(1H-tetrazol-1-yl)ethyl)ethane-1,2-diamine (6), N,N′-(2,2′-azanediylbis(ethane-2,1-diyl))bis(N-(2-(1H-tetrazol-1-yl)ethyl)formamide) (8) and N1-(2-(1H-tetrazol-1-yl)ethyl)-N2-(2-(2-(1H-tetrazol-1-yl)ethylamino)ethyl)ethane-1,2-diamine (9)] ligands have been developed. 2 (whose crystal structure is described), 3, 5, 6, 8 and 9 are of particular interest as precursors for further functionalization due to the aldehyde and secondary amine functions, while 2, 5, 8 and 13 are potential synthons for the formation of ditopic ligands for metal–organic framework construction. Unexpected instability of Boc under basic and nucleophilic conditions at high temperature followed by fragmentation of tert-butyl 2-chloroethyl(2-(2-chloroethylamino)ethyl)carbamate (14) and tert-butyl 2,2′-azanediylbis(ethane-2,1-diyl)bis(2-chloroethylcarbamate) (15) afforded 13, whose crystal structure is presented.