Wiring terpyridine : approaches to alkynylthienyl 2,2 ':6 ',2 ''-terpyridines

Constable, Edwin C. and Figgemeier, Egbert and Housecroft, Catherine E. and Kokatam, Swarna Latha and Medlycott, Elaine A. and Neuburger, Markus and Schaffner, Silvia and Zampese, Jennifer A.. (2008) Wiring terpyridine : approaches to alkynylthienyl 2,2 ':6 ',2 ''-terpyridines. Dalton Transactions, 6 (47). pp. 6752-6762.

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Official URL: http://edoc.unibas.ch/dok/A5251513

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The reaction of triisopropylsilylethyne or trimethylsilylethyne with 4'-(5-bromo-2-thienyl)-2,2' :6',2 ''-terpyridine (1) leads to 4'-(5-triisopropylsilylethynyl-2-thienyl)-2,2':6',2 ''-terpyridine (3) or 4'-(5-trimethylsilylethynyl-2-thienyl)-2,2':6',2 ''-terpyridine (4). The latter compound may be deprotected to give 4'-(5-ethynyl-2-thienyl)-2,2':6',2 ''-terpyridine (5). Treatment of the complexes [Ru(1)(2)][PF6](2), [Ru(tpy)(1)][PF6](2) and [Ru(2)(2)][PF6](2) (2 = 4'-(4-bromo-2-thienyl)-2,2':6',2 ''-terpyridine) with triisopropylsilylethyne yields the corresponding homoleptic and heteroleptic alkynylthienyl-terminated ruthenium(II) complexes, for which spectroscopic and electrochemical data are presented. The reaction of [RuCl2(DMSO)(4)] with 5 leads to [Ru(5)(2)][PF6](2), in which the tpy ligands bear conjugated thienyl and alkynyl groups; the latter can also be accessed by deprotection of [Ru(3)(2)][PF6]2. The single-crystal structures of ligands 2 and 4, and of [Ru(1)(tpy)][BPh4](2)center dot 1.3MeCN, [Ru(1)(2)][PF6]2 center dot 2MeNO(2), 2{[Ru(2)(2)][PF6](2)}center dot 5MeCN, [Ru(3)(2)][PF6](2) and [Ru(5)(2)][PF6](2)center dot MeCN are presented, and among the homoleptic complexes, pi-stacking interactions between thiophene and pyridine rings leading to pairs of associated cations provide a common structural motif.
Faculties and Departments:05 Faculty of Science > Departement Chemie > Chemie > Anorganische Chemie (Constable)
05 Faculty of Science > Departement Chemie > Chemie > Anorganische Chemie (Housecroft)
UniBasel Contributors:Constable, Edwin Charles and Housecroft, Catherine Elizabeth
Item Type:Article, refereed
Article Subtype:Research Article
Publisher:Royal Society of Chemistry
Note:Publication type according to Uni Basel Research Database: Journal article
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Last Modified:10 May 2017 07:17
Deposited On:22 Mar 2012 14:06

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