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Isomeric dinuclear gold(I) complexes with highly functionalised ditertiary phosphines: Self-assembly of dimers, rings and 1-D polymeric chains

Lookup NU author(s): Dr Sophie Dale


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An isomeric series of six linear, dinuclear, gold(I) complexes (AuCl) 2{P,P-C6H4N(CH2PPh2) 2(CO2H)(OH)} 6a-6f have been synthesised in high yields (>90%) from AuCl(tht) (tht = tetrahydrothiophene) and the appropriate building blocks C6H4N(CH2PPh2) 2(CO2H)(OH) 3a-3f in CH2Cl2. The diphosphine ligands C6H4N(CH2PPh 2)2 1, 4-CO2HC6H 4N(CH2PPh2)2 2 and their corresponding digold(I) complexes 4 and 5 have also been prepared. Solution NMR (31P{1H}, 1H), FT-IR and microanalytical data are in full agreement with the proposed structures. Single crystal X-ray studies confirm that in each case, compounds 4, 5, 6a-6e are linear, with typical Au-P [2.227(4)-2.2349(17) Å]/Au-Cl [2.271(2)-2.325(4) Å] bond lengths and P-Au-Cl [169.37(1)-179.05(4)°] bond angles. Furthermore these studies demonstrate the relationship between regioselectivity, with respect to the -N(CH2PPh2)2, -CO2H and -OH functionalities around the benzene core, and solid state structures of the gold(I) complexes 6a-6e. In 6a, molecules are associated into pairs through classical intermolecular O-H⋯O hydrogen bonding, whilst in 6b and 6c, dimer pairs are formed using intermolecular O-H⋯;Cl hydrogen bonds. 1-D chains of alternate 20-/22- or 8-/18-membered hydrogen bonded rings are propagated using O-H⋯Cl and/or O-H⋯O hydrogen bonds in compounds 6d and 6e. The Au⋯Au separation decreases from 6.179(3) Å (for 6a) to 3.0722(9) Å (for 6e) suggesting that aurophilicity increases within this series. The X-ray structure of a representative diphosphine 3a is also presented. © The Royal Society of Chemistry 2006.

Publication metadata

Author(s): Smith MB, Dale SH, Coles SJ, Gelbrich T, Hursthouse MB, Light ME

Publication type: Article

Publication status: Published

Journal: CrystEngComm

Year: 2006

Volume: 8

Issue: 2

Pages: 140-149

ISSN (electronic): 1466-8033

Publisher: Royal Society of Chemistry


DOI: 10.1039/b516023e


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