Supramolecular chemistry of gold(I) thiocyanate complexes with thiophene, phosphine and isocyanide ligands, and the structure of 2,6-dimethylphenyl isocyanide

T. Mathieson, A. Schier, H. Schmidbaur

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Abstract

The reaction of equivalent quantities of (L)AuCl (L = tetrahydrothiophene, trimethylphosphine, 2,6-xylyl isocyanide or mesityl isocyanide) and KSCN in CH2Cl2-water gave (L)Au(SCN) in excellent yield. The products were formed through Cl ↔ (SCN) anion exchange in the two-phase systems. Crystals of (THT)Au(SCN) contain short inter-ion Au···Au contacts (3.006 Å) within chain polymers of alternating cations [Au(THT)2]+ and anions [(NCS)2Au]-. The crystal structure of (Me3P)Au(SCN) exhibits dimers based on short Au···Au contacts of 3.099 Å. The dimers appear to aggregate further by long Au···S contacts giving a tetrameric motif. Molecules of (2,6-Me2C6H3NC)Au(SCN) crystallise as flat, centrosymmetric dimers with long intermolecular Au···Au and Au···S contacts. Although the general aurophilic motif of (2,4,6-Me3C6H2NC)Au(SCN) is similar to (2,6-Me3C6H3NC)Au(SCN), its structure has two different dimers formed from similar monomers. The crystal structure of 2,6-Me2C6H3NC was also characterised and (consistent with bonding theory of metal isocyanides) exhibited a C≡N bond which is slightly longer than in the gold(I) complex.

Original languageEnglish
Pages (from-to)1196-1200
Number of pages5
JournalJournal of the Chemical Society. Dalton Transactions
Issue number8
DOIs
StatePublished - 2001
Externally publishedYes

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