The anomalous paramagnetism of iron(III) NN-dialkyldithiocarbamates

Abstract

The magnetic moments of a series of 19 NN-disubstituted dithiocarbamates of iron(III), [Fe(S2C.NR?R")3], are anomalous in that their behaviour is neither "high-" nor "low-spin". Values of μeff. at room temperature lie between 2.62 and 5.83 B.M., the datum for each compound depending on the chemical nature of the substituents R' and R". This anomalous situation persists in benzene or chloroform solution. Cryoscopic and ebullioscopic molecular weight determinations establish that all the compounds are monomeric, which excludes the possibility that the magnetic behaviour arises from the presence of antiferromagnetic exchange interactions of either the inter- or intra-molecular type. These observations strongly support the early and generally overlooked work of Cambi who in 1932 proposed a thermal equilibrium between "magnetic isomers" of spins S = � and S = 5/2 to account for the origin of the magnetic anomaly.

Compounds with intermediate spin. 3. Structure of tris[N,N-bis(2-hydroxyethyl)dithiocarbamato]iron(III) at 150 and 295 K

“…In a compound llke Fe[S2CN(C2H4OH)2] 3 there Introduction. Most solid Fem dithiocarbamates exhibit strongly temperature-dependent magnetic moments (White, Roper, Kokot, Waterman & Martin, 1964;Ewald, Martin, Sinn & White, 1969 is a possibility of hydrogen bonding without including any solvate molecules. We report here the crystal structure of the title compound, (I), at 150 and 295 K and its magnetic moments in the range 80-300 K.…”

Electrospray ionization of neutral metal dithiocarbamate complexes using in-source oxidation

“…18,19 Sodium salts of piperidinedithiocarbamate and 1-methylpiperazinedithiocarbamate were prepared according to Preti and Tosi. 20 Synthesis of sodium diisopropyldithiocarbamate was based on Uhlin and Akerstrom, 21 that of sodium di-nbutyldithiocarbamate was based on Uhlin and Akerstrom 21 and Bailey et al 22 and sodium dicyclohexyldithiocarbamate was prepared according to Hall and Tiekink.…”

On cobalt(II)N,N-diethyldithiocarbamate

“…The spectrum is also extremely similar to that of the complex Co($2COC2H5) 3, which can be made from cobalt(II) salts and potassium ethylxanthate [7]. The dithiocarbamate complex is strictly isomorphous with the black Fe(Et~dtc)a [8]. Its mass spectrum (direct inlet, 220~ 80 eV) shows very strong peaks at m/e 503, which is the base peak and which corresponds to the molecular ion Co(Et2dtc) +, and at 355 and 207 which correspond to the loss of one and two Et2dtc units respectively, together with a large number of smaller peaks below m/e 200.…”