New insights into the constitution of solutions containing labile, polynuclear compounds: an electrospray mass spectrometric study of mercury- and cadmium-rich dithiocarbamato cations
✍ Scribed by Alan M. Bond; Ray Colton; John C. Traeger; Justin Harvey
- Publisher
- Elsevier Science
- Year
- 1993
- Tongue
- English
- Weight
- 796 KB
- Volume
- 212
- Category
- Article
- ISSN
- 0020-1693
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✦ Synopsis
Electrospray mass spectrometry (ESMS) has been used to study the constitutron of mercury and mixed mercury/ cadmium dithiocarbamato cations m dichloromethane and methanol solutions. In all cases the ions observed are of the form {[M(R,dtc)]+ +nM(R,dtc),} (n = 1-3, M=Hg, Cd), e.g. [Hg,(R,dtc),]+ (n = 1). Addition of M(R,dtc), favours formatron of the higher oligomers. Ligand exchange between different mercury dithtocarbamato cations IS fast on the NMR timescale, but ESMS shows the indrvtdual Ions with various hgand combinatrons.
Similarly, reaction of a mercury-rich dithiocarbamato cation with a neutral Cd(R,dtc), complex of a different dithiocarbamate gives global exchange between ligands and metals and ESMS observes mdtvidual Ions in the complex mixture. Exploratory experiments show that a similar chemistry exists for metal-rich drthiophosphate catronic systems. The order observed in these solutions leads to the suggestion that the M(R,dtc), groups act as hgands towards the [M(R,dtc)]+ cations and analogies are proposed between these hgand properties and those of the [MS,]'-(M =Mo, W) anions.