Cyclometallation reactions of 6-(2-thienyl)-2,2′-bipyridine with d8 transiton metal ions

Edwin C. Constable, Roland P.G. Henney, Paul R. Raithby, Lynn R. Sousa

Research output: Contribution to journalArticlepeer-review

Abstract

The potentially terdentate ligand 6-(2-thienyl)-2,2′-bipyridine (Hthbipy) reacts with [MCl4]2- (M = Pd or Pt) under mild conditions to give cyclometallated complexes in which the thienyl ring is metallated at the 3 position. The metallated complexes [M(thbipy)Cl] (M = Pd or Pt) react with trimethyl phosphite to give phosphonate complexes [M(thbipy){P(=O)(OMe)2}] and with Na[acac] (Hacac = acetylacetone) to give [M(thbipy)(acac)] with a C-bonded acac ligand. Under mild conditions, the non-metallated compound [Pd(Hthbipy)Cl2] can be isolated. In contrast, the reaction of Hthbipy with Na[AuCl4] at ambient temperature yields the non-metallated complex [Au(Hthbipy)Cl3], but upon heating this, or performing the reaction at higher temperatures, the metallated compound [Au(thbipy)Cl2] is obtained. X-Ray structural analysis of this complex reveals it to be dimeric where the ligand has metallated at the 5 position of the thienyl ring and adopts a bridging bidentate N,C mode [triclinic, space group P1, a = 9.271(5), b = 14.214(10), c = 16.194(10) Å, α = 108.11(5), β = 96.55(5), γ = 111.46(5)°, Z = 2, R = 0.075, R′ = 0.094].

Original languageEnglish
Pages (from-to)2251-2258
Number of pages8
JournalJournal of the Chemical Society, Dalton Transactions
Issue number14
DOIs
Publication statusPublished - 1992

ASJC Scopus subject areas

  • General Chemistry

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