Reaction of Methanol with Diphenylantimony(V) Trihalides: Crystal Structure of 2

Article abstract of DOI:10.1039/DT9940001983

A re-examination of the reaction between diphenylantimony trichloride and methanol showed that the initial product is a methanol adduct of the monomethoxide, SbPh2Cl2(OMe), rather than the oxide (SbPh2Cl2)2O, which is a hydrolysis product formed during recrystallisation.The corresponding tribromide, and the mixed halides, SbPh2Br(3-n)Cln, where n=1 or 2, react similarly with methanol, losing a bromine atom to give solvated monomethoxy products.X-Ray diffraction analysis revealed that SbPh2Br2(OMe) crystallises as a centrosymmetric dimer, incorporating two molecules of methanol, which are attached via strong hydrogen bonds to the oxygen bonds to the oxygen atoms of the methoxy groups.Co-ordination of the methanol oxygen to a symmetry-related antimony atom completes the distorted-octahedral co-ordination about antimony and forms a central eight-atom ring system in the chair conformation.Two unusual features are the similarity of the two Sb-O distances <2.101(4) and 2.121(4) Angstroem>, even though the former is formally a normal ? bond and the latter a donor linkage, and the presence of a weak ?-arene...H-C hydrogen bond, which probably accounts for the orthogonality of the phenyl groups at antimony.

Full text of DOI:10.1039/DT9940001983

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