Structural and X-ray photoelectron spectroscopic properties of hydrophobic cobalt(III) 'cage' complexes with dithiocarbamate anions
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The X-ray photoelectron spectra of the hydrophobic encapsulated cobalt(III) complexes, [Co(diNOsar)][S2CNR2]3, are reported, together with a single crystal X-ray structure determination of [Co(diNOsar)][S2CN(CH2)4]3 (diNOsar=1,8-dinitro-3,6,9,13,16,19-hexaazabicyclo[6.6.6.]icosane; S2CNR2=N,N-dialkyldithiocarbamate). Results show that the Co 2p3/2 binding energy (BE) for the complex cation of 780.5 eV is not significantly different to the BE found for [Co(en)3]Cl3 but is ca. 1.4 eV greater than the values recorded for Co(S2CNR2)3 complexes. Similarly, S 2p BE values are relatively constant for each anion (range 160.8-161.3 eV), but less than the values of 161.9-162.2 eV recorded for Co(S2CNR2)3. Crystals of [Co(diNOsar)][S2CN(CH2)4]3 are monoclinic, space group C2/c with a = 34.526(7), b = 11.071(2), c = 23.445(3) Šand ߠ= 96.37(1)The structure refined to a final R value of 0.065 for 2754 observed (I>2.5s(I)) reflections. Strong hydrogen bonds exist between the sulfur atoms of the dithiocarbamate anion and the secondary amine protons of the complex cation which is stabilized in a C3lel3 conformation by these interactions.
Inorganica Chimica Acta
Copyright 1989 Elsevier. Please refer to the journal's website for access to the definitive, published version.