Simple mercury-free synthesis and characterization of symmetric and unsymmetric mono- and dialkynyl (tpy)Au(III) complexes

• Verfasst von: Witzel, Sina [VerfasserIn]
• Verfasst von: Holmsen, Marte S. M. [VerfasserIn]
• Verfasst von: Rudolph, Matthias [VerfasserIn]
• Verfasst von: Dietl, Martin C. [VerfasserIn]
• Verfasst von: Øien-Ødegaard, Sigurd [VerfasserIn]
• Verfasst von: Rominger, Frank [VerfasserIn]
• Verfasst von: Tilset, Mats [VerfasserIn]
• Verfasst von: Hashmi, A. Stephen K. [VerfasserIn]
• Titel: Simple mercury-free synthesis and characterization of symmetric and unsymmetric mono- and dialkynyl (tpy)Au(III) complexes
• Verf.angabe: Sina Witzel, Marte S. M. Holmsen, Matthias Rudolph, Martin C. Dietl, Sigurd Øien-Ødegaard, Frank Rominger, Mats Tilset, and A. Stephen K. Hashmi
• E-Jahr: 2020
• Jahr: July 28, 2020
• Umfang: 8 S.
• Fussnoten: Gesehen am 16.09.2020
• Titel Quelle: Enthalten in: Organometallics
• Ort Quelle: Washington, DC : ACS Publ., 1982
• Jahr Quelle: 2020
• Band/Heft Quelle: 39(2020), 15, Seite 2830-2837
• ISSN Quelle: 1520-6041
• DOI: doi:10.1021/acs.organomet.0c00364
• Datenträger: Online-Ressource
• Sprache: eng
• K10plus-PPN: 1733104976

Abstract

A highly efficient mercury-free route, providing [C^N] cyclometalated symmetric dialkynyl gold(III) complexes with 2-(p-tolyl)pyridine (tpy) as bidentate ligands and using alkynyllithium reagents, was developed. With 1,9-decadiyne, an unprecedented representative of a di(bidentate) gold(III) complex, for the first time became accessible. By using Grignard instead of the alkynyllithium reagents, we succeeded in synthesizing a range of novel monoalkynyl gold(III) complexes in excellent yields (74-92%) and diastereoselectivity. Treating [(tpy)Au(C≡CTMS)2] with Bu4NF in THF gave a complete deprotection, and with K2CO3 in methanol, there was a selective deprotection of the TMS group trans to the pyridyl N atom, providing [(tpy)Au(C≡CH)(C≡CTMS)] as the major product. This new type of cyclometalated gold(III) complex bears two different alkynes as ancillary ligands. The further functionalization of the monoalkynyl (tpy)gold(III) complexes was investigated, offering a universal unprecedented and diastereoselective access to unsymmetrical dialkynyl (tpy)gold(III) complexes.