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The Effect of Hard and Soft Donors on Structural Motifs in (Isocyanide)gold(I) Complexes
Author(s) -
WiltonEly James D. E. T.,
Ehlich Hendrik,
Schier Annette,
Schmidbaur Hubert
Publication year - 2001
Publication title -
helvetica chimica acta
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.74
H-Index - 82
eISSN - 1522-2675
pISSN - 0018-019X
DOI - 10.1002/1522-2675(20011017)84:10<3216::aid-hlca3216>3.0.co;2-7
Subject(s) - chemistry , isocyanide , quinoline , pyridine , yield (engineering) , cationic polymerization , gold compounds , stereochemistry , halide , crystal structure , medicinal chemistry , crystallography , polymer chemistry , combinatorial chemistry , organic chemistry , materials science , metallurgy
Treatment of the (isocyanide)gold(I) species LAuCl (L= t BuNC, 2,6‐Me 2 C 6 H 3 NC) with 4‐mercaptobenzoic acid in the presence of NaOMe yields the complexes [Au(4‐SC 6 H 4 CO 2 H)L] in good yield. Reaction of LAuCl with 2‐HSQn (Qn=quinoline) and 2‐HSPy (Py=pyridine) under the same conditions provides the thiolato compounds [Au(2‐SQn)L] and [Au(2‐SPy)L], respectively. A structural investigation of the pyridylthiolato compound revealed chains of molecules with alternating medium and long Au−Au interactions. Treatment of this compound with HBF 4 results in the cationic species [Au(2‐HSPy)(2,6‐Me 2 C 6 H 3 NC)] + as the BF 4 − salt. The same product is obtained on reaction of [AuCl(2,6‐Me 2 C 6 H 3 NC)] with AgOTf followed by HSPy. Treatment of the gold(I) halide compounds LAuCl (L= t BuNC, 2,6‐Me 2 C 6 H 3 NC) with potassium 1,3,4‐thiadiazole‐2,5‐dithiolate (KSSSK) leads to the isolation of dinuclear thiolatogold complexes [(AuL) 2 (SSS)]. These products go on to form insoluble polymers through loss of isocyanide on standing in solution. A single crystal of [{Au( t BuNC)} 2 (SSS)] was obtained and the subsequent structural analysis revealed one of the most complicated networks known based solely on aurophilic interactions. A good comparison to the ‘soft' S‐donation of the thiolato ligands was provided by the synthesis of a number of nitratogold(I)complexes with the anion bound through the ‘hard' O‐donor. Reaction of i PrNC and CyNC with Au(tht)Cl provided the complexes [AuCl( i PrNC)] and [AuCl(CyNC)], respectively. These compounds were found to yield the respective nitrato species [Au(NO 3 ) i PrNC)] and [(Au(NO 3 )(CyNC)] on treatment with AgNO 3 . The nitrato complexes yielded single crystals enabling a structural investigation to be carried out. While [Au(NO 3 )(CyNC)] has a more conventional structure with dimers aligned into strings with alternating short and long aurophilic bonding, [Au(NO 3 )( i PrNC)] has a unique structure based on strings of alternating, corner‐sharing Au 6 and Au 8 units with short Au−Au contacts in edge‐sharing Au 3 triangles.