Lukáš Jeremias

Synthesis and X-Ray Structures of Zinc(II) and Cadmium(II) Heteroleptic Complexes Involving 1,1-Dithiolate and N-Donor Ligands

GRAPHICAL ABSTRACT Abstract A series of zinc(II) and cadmium(II) complexes, involving a combination of S–donor (xanthates and dithiophosphates) and N-donor (1,10-phen = 1,10-phenanthroline, 2,2′–bipy = 2,2′-bipyridine) ligands, of the composition [Cd(S2COnPr)2(2,2′-bipy)] (1), [Cd(S2COnPr)2(1,10-phen)] (2), [Cd(S2P(OEt)2)2(2,2′-bipy)] (3), [Cd(S2P(OEt)2)2(1,10-phen)] (4), [Zn(S2COnPr)2(2,2′-bipy)] (5), [Zn(S2COnPr)2(1,10-phen)] (6), [Zn(S2P(OEt)2)2(2,2′-bipy)] (7), and [Zn(S2P(OEt)2)2(1,10-phen)] (8) was prepared. The complexes (1–8) were characterized by elemental analysis and single-crystal X-ray analysis. X-ray structures revealed that the coordination geometries vary from octahedral (complexes 1–4), through square-pyramidal (complexes 5 and 6) to tetrahedral (complexes 7 and 8), depending on a combination of the central metal atoms and the corresponding S-donor and N-donor ligands. Similarities and discrepancies among the individual molecular structures as well as noncovalent contacts stabilizing crystal structures are discussed in more detail.

X-ray structures of heteroleptic zinc(II) complexes involving combinations of O,O'-dialkyldithiophosphato and bidentate N-donor ligands

Abstract The detailed X-ray structural elucidation of reaction products of a zinc(II) salt with O,O′-dialkyldithiophosphate and nitrogen-containing heterocycles (N–N=1,10-phenanthroline (phen) or 2,2′-bipyridine (bpy)) has been performed. Surprisingly, together with [Zn(S2 P(OR)2)2(N–N)] compounds, also ionic-type complexes having the formula of [Zn(N–N)3](S2 P(OR)2)2 have been obtained using the same molar ratios of the reactants. The prepared complexes have been characterized by elemental analysis and single-crystal X-ray analysis. The crystallographic analysis showed that the bond lengths and bite angles of the prepared complexes are in good agreement with those of similar compounds. The crystal packing of described complexes is formed via π–π stacking interactions and/or C–H···S non-covalent contacts.

Successful oxidation of Ph 2 P(CH 2 ) n PPh 2 ( n = 2, 4, 6) by tellurium leading to Ph 2 P(Te)(CH 2 ) n P(Te)Ph 2

The first successful syntheses of Ph2P(Te)(CH2)nP(Te)Ph2 (n = 2, 4, 6) via oxidation of Ph2P(CH2)nPPh2 by tellurium powder are reported. The prepared compounds were characterized by elemental analysis, 31P and 125Te NMR spectroscopy, and single-crystal X-ray analysis.

Synthesis and structure of tris(dimethyldithiocarbamato)(1,10-phenanthroline)lanthanide complexes

Abstract Syntheses and structures of three new lanthanide coordination compounds with dithiocarbamate ligands are reported. The complexes [Ln(Me2dtc)3(phen)] (Ln = Pr (1), Nd (2) and Gd (3), Me2dtc = N,N-dimethyldithiocarbamate and phen = 1,10-phenanthroline) were synthetized by a simple metathesis between lanthanide(III) nitrate and sodium dimethyldithiocarbamate followed by addition of 1,10-phenanthroline without the exclusion of moisture. Single crystal X-ray analysis showed that all three complexes are isostructural, crystallizing in the triclinic space group P1̅. The Ln-S and Ln-N bond lengths decrease in agreement with the decrease in ionic radii across the lanthanide series. Similar structures with Et2dtc ligands show no significant effect on the changes of Ln-S bond lengths and also on the S-Ln-S bite angles. The crystal packing of described complexes is formed via π-π stacking interactions and C-H ... S non-covalent contacts.

Syntheses and X-ray structures of heteroleptic octahedral Mn(II)-xanthato complexes involving N-donor ligands

A series of octahedral manganese(II) complexes involving xanthates and N-donor ligands, [Mn(S2COiBu)2(phen)] (1), [Mn(S2COiBu)2(2,2′-bpy)] (2), [Mn(S2COnPr)2(phen)] (3), [Mn(S2COnPr)2(2,2′-bpy)] (4), [Mn(S2COMe)2(2,2′-bpy)] (5), [Mn(S2COnPr)2(4,4′-bpy)]n, and [Mn2(S2COnPr)4(4,4′-bpy)3] (6) (phen = 1,10-phenanthroline, bpy = bipyridine) was prepared. Complexes were characterized by elemental analysis, FTIR spectroscopy, TG/DSC analysis, and single-crystal X-ray diffraction. The structures are built of monomeric molecules of the complexes, except for 6 with the 4,4′-bipyridine ligand, which contains a binuclear complex and 1D polymeric zigzag chain in one crystal.