| Popis: |
Reactions of MoCl 3 (THF) 3 and MoCl 3 (PrCN) 3 with the macrocyclic polythiaethers: 1,4,8,11-tetrathiacyclotetradecane (TTP) and 1,4,7,10,13,16-hexathiacyclooctadecane (HTO) were studied. The type of reaction and the complexes formed depend on reactant concentration and nature of the solvent. The complexes: [MoCl 3 (HTO)], [(MoCl 3 ) 2 (HTO)(THF) 3 ], [MoCl 3 (TTP)(THF)] and [MoCl 3 (TTP)] in which the macrocyclic polythiaethers are coordinated to the molybdenum through sulphur atoms were isolated. Some new mixed-valence complexes were formed in reactions where a partial change in the molybdenum oxidation state and a cleavage of the macrocyclic ring took place. The following complexes were isolated: [Mo 3 Cl 9 (PHT) 2 (PrCN)]·CH 2 Cl 2 , [Mo 3 Cl 9 (PHT) 2 (THF)] · CH 2 Cl 2 , [Mo 2 Cl 6 (PHT)] · CH 2 Cl 2 , [Mo 3 Cl 9 (TTT) 2 (THF)] · CH 2 Cl 2 , where PHT = 3,6,9,12,15-pentathiaheptadec- 16-ene-1-thiolato(1-) and TTT = 4,7,11-trithiatridec-12-ene-1-thiolato(1-). The complexes were characterized on the basis of elemental analyses, magnetic measurements, IR, 1 H NMR, 13 C NMR and mass spectra. |
