Structural correlations between trans- and cis-bis(diphenylphosphino)ethene, bis(diphenylphosphino)methane and their chlorogold(I) complexes

Hubert Schmidbaur, Gabriele Reber, Annette Schier, Friedrich E. Wagner, Gerhard Müiller

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85 Scopus citations

Abstract

The crystal structures of trans- and cis-bis(diphenylphosphino) ethene (1, 2) have been determined by single crystal X-ray diffraction. The conformation of these free ligands is compared with structural data available in the literature for the corresponding 1:2 complexes with gold(I) chloride (4, 5). In the cis-ligand 2 the conformation of the Ph2P-groups is such, that the molecule approaches non-crystallographic Cs symmetry with the lone pairs at phosphorus pointing towards each other. Upon addition of AuCl, rotation of one Ph2P group around the PC bond by approximately 60° leads to a structure for 5 which allows an intramolecular Au···Au contact of 3.05(1)Å. The trans-ligand 1 undergoes little structural change upon adduct formation, but intermolecular Au···Au contacts of 3.043(1) Å are secured through aggregation. The synthesis, properties and 197Au Mössbauer spectra of 1:1 and 1:2 complexes of 1 and 2 with AuCl are summarized with reference to a recent controversy in the literature. The crystal structure of bis(diphenylphosphino)- methane (3) has also been determined and the results compared with those published previously for the 1:2 complex with AuCl (7, crystallographic C2 symmetry, Au···Au distance 3.351(2) Å). There is very little change of the ligand conformation upon coordination.

Original languageEnglish
Pages (from-to)143-150
Number of pages8
JournalInorganica Chimica Acta
Volume147
Issue number2
DOIs
StatePublished - 15 Jul 1988
Externally publishedYes

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