77900-40-4Relevant academic research and scientific papers
Tri- and di-arylantimony( V) thiocyanates and mixed halide thiocyanates; crystal structure of triphenylantimony( V) di-isothiocyanate
Forster, Glynis E.,Begley, Michael J.,Sowerby, D. Bryan
, p. 263 - 274 (2007/10/03)
A series of triarylantimony(V) dithiocyanates has been prepared by oxidising the appropriate antimony(III) compound with thiocyanogen. IR and 14N NMR spectroscopy indicate the presence of terminally N-bonded thiocyanate groups and this has been confirmed by a crystal structure determination for the SbPh3(NCS)2. The asymmetric unit contains three independent trigonal bipyramidal molecules, which differ in the orientations of the axial N-bonded thiocyanates and the phenyl groups in the equatorial plane, and there may be weak C-H ... S interactions. Treatment of SbPh2X3, where X = Br or Cl, with KSCN gave K[SbPh2(NCS)4] and attempts to prepare SbPh2(NCS)3 and related diphenylantimony(V) mixed halide thiocyanates, SbPh2Xn(NCS)3 - n where X = Br or Cl and n = 0-2, by treating appropriate diphenylantimony(III) precursors with thiocyanogen or thiocyanogen bromide or chloride gave products which in many cases underwent reorganisation during recrystallisation. Samples of SbPh2(NCS)3, SbPh2Br(NCS)2, SbPh2Br2(NCS) and SbPh2Cl2(NCS), and SbPh3Br(NCS) have, however, been isolated as microcrystalline solids.
Preparation and Crystal Structures of Diphenylantimony(III) Thiocyanate and Bis(2,6-dimethylphenyl)antimony(III) Thiocyanate
Forster, Glynis E.,Begley, Michael J.,Sowerby, D. Bryan
, p. 377 - 382 (2007/10/02)
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.
