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Toluene-3,4-dithiol (H2tdt) Complexes of Group 5B Halides. Observations of Lone-pair Stereochemical Activity and Redox Behaviour. Crystal and Molecular Structures of and

DOI: 10.1039/DT9850000069

Source and publish data:

Journal of the Chemical Society, Dalton Transactions p. 69 - 74 (1985)

Update date:2022-08-03

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Authors:

Kisenyi, Jonathan M.Kisenyi, Jonathan M.

Willey, Gerald R.Willey, Gerald R.

Drew, Michael G. B.Drew, Michael G. B.

Wandiga, Shem O.Wandiga, Shem O.

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Article abstract of DOI:10.1039/DT9850000069

Reactions of toluene-3,4-dithiol (H2tdt) with the Group 5B chlorides MCl3 (M=As, Sb or Bi) have been investigated under conditions of varying stoichiometry.Complexes of the types (M=As, Sb, or Bi), , , and (Y=NEt4 or PPh4) have been isolated and characterised by spectroscopic (i.r. and 1H n.m.r.) data.For the series, obtained following 1:1 addition, ligand (SH) protons are removed as HCl and a tetrahedral geometry with full stereochemical participation of the lone pair of electrons associated with M(III) is confirmed for M=As by an X-ray crystal structure determination.The complexes and , resulting from 1:2 addition, are quite dissimilar with only the latter experiencing full replacement of ligand (SH) protons.For there is strong evidence to suggest that one of the ligand (SH) protons remains intact giving rise to a neutral species based on Sb(III).Attempts to remove this proton to give the anion - have been unsuccessful.For the complexes, obtained following 1:3 addition, all ligand (SH) protons are removed and an X-ray crystal structure determination for Y=PPh4 shows the anion as a slightly distorted octahedron following aerial oxidation Sb(III)->Sb(V).Crystals of (1) are monoclinic, space group P21/c, Z=4, a=6.127(5), b=15.773(11), c=9.768(8) Angstroem, and β=91.0(1) deg.Crystals of (2) are monoclinic, space group P21, Z=2, a=10.464(7), b=12.825(9), c=16.433(8) Angstroem, and β=102.5(1) deg. 1113,884 Reflections above background have been collected on a diffractometer and the structures refined to R 0.052, 0.120 respectively.In (1) the arsenic atom is three-co-ordinate .In -, the antimony atom is six-co-ordinate in a distorted octahedral environment with Sb-S in the range 2.34(3)-2.50(2) Angstroem.

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