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Cobalt(II) and Nickel(II) Trithiocarbonate Complexes as Nucleophilic Reagents. Reactivity and X-Ray Structure of the Trithiocarbonate Complex *1.5thf

DOI: 10.1039/DT9820000799

Source and publish data:

Journal of the Chemical Society, Dalton Transactions p. 799 - 804 (1982)

Update date:2022-09-26

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Authors:

Bianchini, ClaudioBianchini, Claudio

Mealli, CarloMealli, Carlo

Meli, AndreaMeli, Andrea

Scapacci, Gian CarloScapacci, Gian Carlo

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Article abstract of DOI:10.1039/DT9820000799

The trithiocarbonate complexes and are highly activated toward electrophilic reagents.The unco-ordinated sulphur atom is found to displace the halide ion from alkyl halides or weakly bound ligands from other organometallic derivatives to give sulphur alkylated cations or CS3-bridged binuclear complexes respectively.The crystal and molecular structure of the trithiocarbonate complex *1.5 thf has been determined by standard X-ray methods.The compound is monoclinic, space group C2/c, Z=8, a=42.420(7), b=10.221(4), c=35.449(7) Angstroem, β=124.93(8) deg.The complex cation is five-co-ordinated by the three phosphorus of the tppme ligand and two sulphur atoms of the trithiocarbonate anion.The latter group can be considered planar, the methyl carbon atom almost lying in the CS3 plane.The bonding between the Co(tppme) and S2CS fragments is analysed in terms of qualitative molecular orbital arguments.This trithiocarbonate complex udergoes lidand nucleophilic substitution with diethylamine to form the dithiocarbamate complex *0.5CH2Cl2.

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