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Diphosphanegold(I) complexes of the form dppm E AuX [dppm = bis(diphenylphosphano)methane,  E  = S, Se; X = Br, I], dppe E AuX [dppe = 1,2-bis(diphenylphosphano)ethane;  E  = O, S; X = Br, I] and dppbz E AuX [dppbz = 1,2-bis(diphenylphosphano)benzene;  E  = S, Se, X = Br, I] were treated with elemental X 2 . With dppm, the three products [dppm E AuX 2 ] + X 3  –  ( E  = S, X = Br ( 1 ), I ( 2 );  E  = Se, X = I ( 3 ) were obtained in quantitative yield. These are gold(III) complexes involving a five-membered ring   . With dppe, the only related product was [dppe E AuBr 2 ] + Br 3  –  ( 4 ), in which the central ring is six-membered with two carbon atoms. These dppe systems are very sensitive to oxidation/hydrolysis of the ligand, and several such unintended products were isolated and identified. The reaction of dppbzSAuBr with bromine leads to [dppbzS] 2+ [AuBr 4 ] – Br –  ( 5 ), the dication of which is formally 1,1,3,3-tetraphenylbenzo[ d ]-2-thia-1, 3-diphosphol-1,3-diium and contains a central five-membered ring   . The dications are associated with the bromide anions  via  S…Br contacts of ca. 3.1 Å to form inversion-symmetric S 2 Br 2  rings. The halogenation of the dppbzSe derivatives leads to loss of selenium and formation of dppbzAuBr 3  ( 6 ), with [4+1] coordination at gold, or the known compound [dppbzAuI 2 ] + I 3  –  ( 7 ). All products  1 – 6  were subjected to X-ray diffraction analyses, as were four hydrolysis products  4a – d  and two further by-products [5(thtBr + )·2Br 3  – ·3(AuBr 4  – )] ( 1a ) and (tht)AuBr 3  ( 1b ). Compound  1a  displays unusually short Br…Br contacts of 3.2398(8) Å between neighbouring tetrabromidoaurate(III) ions.

Phosphanchalkogenide und ihre Metallkomplexe. IV. Halogenierungsprodukte der Gold(I)halogenidkomplexe einiger Diphosphanmonochalkogenide