51525-62-3Relevant articles and documents
New square-pyramidal organoantimony(v) compounds; crystal structures of (biphenyl-2,2′-diyl)phenylantimony(v) dibromide, dichloride and diisothiocyanate, Sb(2,2′-C12H8)PhX2 (X = Br, Cl or NCS), and of octahedral SbPh(o-O2C6Cl4)Cl2·OEt 2
Gibbons, Martin N.,Begley, Michael J.,Blake, Alexander J.,Sowerby, D. Bryan
, p. 2419 - 2425 (2007/10/03)
Oxidative addition between (biphenyl-2,2′-diyl)phenylantimony(III), Sb(2,2′-C12H8)Ph 1 and Br2 or SO2Cl2 gave Sb(2,2′-C12H8)PhBr2 2 and Sb(2,2′-C12H8)PhCl2 3, respectively, while the corresponding fluoride Sb(2,2′-C12H8)PhF2 4 and the thiocyanate Sb(2,2′-C12H8)Ph(NCS)2 5 were obtained by metathesis reactions between 3 and KF and KSCN, respectively. Compounds 2 and 3 are isostructural but, in contrast to the closely related SbPh3X2 species, individual molecules have square-pyramidal geometry. Again in contrast to SbPh3X2 compounds, secondary antimony-halogen interactions trans to the apical carbon atom lead to solid-state dimers, implying Lewis acidity at antimony. Antimony in the thiocyanate 5 snowed similar square-pyramidal geometry with N-bonded thiocyanate groups but bridging by one thiocyanate again gives dimers in the solid. Oxidative addition between SbPhCl2 and tetrachloro-ortho-benzoquinone in ether solution gave the tetrachlorocatechol analogue of 3 as a six-co-ordinate ether solvate, SbPh(o-O2C6Cl4)·OEt2 6. If the weak bond to ether is ignored, antimony again has square-pyramidal geometry but formation of the adduct again points to antimony Lewis acidity. A non-solvated substituted catecholate, SbPh(o-O2C6H2But 2-3,5)Cl2 8, was also synthesized but crystals suitable for X-ray diffraction could not be obtained.
