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Preparation and Crystal Structures of Diphenylantimony(III) Thiocyanate and Bis(2,6-dimethylphenyl)antimony(III) Thiocyanate

DOI: 10.1039/DT9950000377

Source and publish data:

Journal of the Chemical Society, Dalton Transactions p. 377 - 382 (1995)

Update date:2022-08-03

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Authors:

Forster, Glynis E.Forster, Glynis E.

Begley, Michael J.Begley, Michael J.

Sowerby, D. BryanSowerby, D. Bryan

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Article abstract of DOI:10.1039/DT9950000377

Diphenylantimony(III) and bis(2,6-dimethylphenyl)antimony(III) tiocyanates have been prepared by metathesis reactions between the appropriate diarylantimony(III) halide and potassium thiocyanate in acetonitrile solution.The second compound was also obtained by thermal decomposition of tris(2,6-dimethylphenyl)antimony(V) dithiocyanate.Crystal structure determinations showed that in SbPh2(NCS) the thiocyanate group bridges between antimony centres to give an infinite polymer, while the 2,6-dimethyl-substituted analogue is an N-bonded monomer.The diphenylantimony structure is probably unique in that the asymmetric unit consists of three formula units and, although each thiocyanate group is bridging, two are primarily N-bonded while the third is primarily S-bonded.Angles at the bridging nitrogens are large (150.4-174.9 deg) while those at sulfur are close to 90 deg (85.7-98.6 deg).These in conjunction with the presence of thiocyanate groups in the axial positions of pseudo-trigonal-bipyramidal arrangements about antimony lead to a curious 'triangular spiral' structure for the polymeric chains.

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