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Gold Coordination by Tertiary Phosphane Sulfides
Author(s) -
Preisenberger Max,
Bauer Andreas,
Schmidbaur Hubert
Publication year - 1997
Publication title -
chemische berichte
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 0009-2940
DOI - 10.1002/cber.19971300723
Subject(s) - chemistry , tetrahydrothiophene , bromide , sulfur , cationic polymerization , reagent , sulfonium , medicinal chemistry , metathesis , salt metathesis reaction , chloride , crystal structure , atom (system on chip) , crystallography , stereochemistry , inorganic chemistry , organic chemistry , salt (chemistry) , computer science , embedded system , polymerization , polymer
Treatment of the ditertiary phosphane sulfides (CH 2 ) n [PPh 2 S] 2 , 1a – 1d , n = 1‐4, with equivalent amounts of (dimethylsulfide)gold(I) chloride (Me 2 S)AuC1 affords the dinuclear complexes 2a–2d with an AuCl unit attached to each sulfur atom. The chlorides can be converted into the bromides 3a–3c by metathesis using KBr, or by reacting 1d with (tetrahydrothiophene)gold bromide. With [(Ph 3 P)Au] + O 3 SCF 3 as the aurating agent for the diphosphane disulfides, the corresponding dicationic products are obtained: {(CH 2 ) n [SPPh 2 AuPPh 3 ] 2 } 2+ · 2 O 3 SCF 3 ( 4b‐4d , n = 2‐4). An excess of the reagents does not lead to polygold clustering at the sulfur atoms, and P‐S cleavage occurs instead to give sulfonium salts {S[Au(PPh 3 )] 3 } + X − . The reaction of Ph 3 PS with equimolar quantities of [ (Ph 3 P)Au]O 3 SCF 3 leads to the cationic 1:1 complex 5 , and with an excess of the agent the P–S bond is ruptured. The structures of compounds 4b and 4d were determined by single‐crystal X‐ray diffraction. The dications have crystallographic centers ot inversion, the coordination at the gold atoms is linear [ 4b : 179.03(3)° 4d : 175.29(2)°] and the angles at the sulfur atoms are acute [ 4b : 97.76(4)° 4d : 96.37(3)°], but there are no short Au–Au contacts.