TY - JOUR
T1 - Cyclometallation reactions of 6-(2-thienyl)-2,2′-bipyridine with d8 transiton metal ions
AU - Constable, Edwin C.
AU - Henney, Roland P.G.
AU - Raithby, Paul R.
AU - Sousa, Lynn R.
PY - 1992
Y1 - 1992
N2 - 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].
AB - 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].
UR - http://www.scopus.com/inward/record.url?scp=37049080939&partnerID=8YFLogxK
U2 - 10.1039/DT9920002251
DO - 10.1039/DT9920002251
M3 - Article
AN - SCOPUS:37049080939
SN - 1472-7773
SP - 2251
EP - 2258
JO - Journal of the Chemical Society, Dalton Transactions
JF - Journal of the Chemical Society, Dalton Transactions
IS - 14
ER -