Abstract
This thesis describes the preparations, magnetic, Mossbauer, and other investigations of some new iron(II) complexes of various xanthate anions ROCS[2](Rxn), where R = cyclohexyl (Ch), 2-methylcyclohexyl(2-Me-Ch), Me or Et. All complexes were handled under nitrogen or in vacuo because they are very air-sensitive. The adducts Fe(Chxn)[2] L[2], where L = methanol, ethanol, pyridine, 3-methylpyridine, 4-methylpyridine, 3,5-lutidine, 3,5-dichloropyridine, or iso-quinoline have been found to be magnetically-normal, high-spin, distorted octahedral iron (II) complexes. The complexes Et[4]N[Fe(Chxn)[3]] and Bu[4]N[Fe(Chxn)[3]] were prepared for comparison and they also contain high-spin iron (II), but, as expected from the presence of six identical donor atoms, have smaller quadrupole splittings than the base adducts. Mossbauer spectra of the complex Fe(Chxn)[2] (3,5-lutidine)[2] prepared by one method showed four peaks indicating that two iron sites were present, but a different preparative procedure gave a product showing only two peaks. The complexes Fe(Chxn)[2] and Fe(2-Me-Chxn)[2]. H[2]O are antiferromagnetic and are believed to be S-bridged polymers. Mossbauer investigations of Fe(Chxn)[2] showed that two iron sites are present. This may be due to the simultaneous presence of five-coordinate dimers and six-coordinate polymers. The complexes Fe (Mexn)[2](py)[2] and Fe(Etxn)[2](py)[2] have been isolated as solids for the first time. Various investigations, including X-ray powder photography, have confirmed that the dithiocarbamato-complexes Fe(R[2]NCS[2])[2] fall into two classes according to the nature of the R group. When R = Et, Pr[n], or Bu[n], a dimeric five coordinate structure is suggested from the very large quadrupole splittings (4.2 mm s[-1]) obtained. When R = CH[3] or R[2] = C[4]H[8] co-ordinate structure is suggested by the smaller quadrupole splittings (~2.5 mm s[-1]). Complexes of o-aminobenzenethiol Fe(C[6]H[4]NH[2]S)[2], [2]-mercaptoethylamine Fe(NH[2]CH[2]CH[2]S)[2]. H[2]O, dicyclo-hexyldithiophosphate Fe[(C[6]H[11]O)[2]PS[2]][2], and dicyclopentyldithiophosphate Fe[(C[5]H[9]O)[2]PS[2]][2] have been obtained. The first two compounds have been shown to be antiferromagnetic, and the others were magnetically-normal. The diamagnetic nitrosyls Fe(Rxn)[2](NO)[2], in which R = ethyl, methyl and cyclohexyl, have also been isolated. Their infrared spectra suggest cis-configurations. Some Schiff's Base-iron nitrosyls of the type Fe-salen NO where salen = NN'-ethylene bis(salicylid-eneimine have been re-investigated.