TY - JOUR
T1 - Bis(bipyridine)ruthenium(II) complexes with an aliphatic sulfinato donor
T2 - Synthesis, characterization, and properties
AU - Tamura, Motoshi
AU - Tsuge, Kiyoshi
AU - Igashira-Kamiyama, Asako
AU - Konno, Takumi
PY - 2011/6/6
Y1 - 2011/6/6
N2 - Treatment of a thiolato-bridged RuIIAgIRu II trinuclear complex, [Ag{Ru(aet)(bpy)2} 2]3+ (aet = 2-aminoethanthiolate; bpy = 2,2'-bipyridine), with NaI in aqueous ethanol under an aerobic condition afforded a mononuclear ruthenium(II) complex having an S-bonded sulfinato group, [1]+ ([Ru(aesi-N, S)(bpy)2]+ (aesi = 2-aminoethanesulfinate)). Similar treatment of optically active isomers of an analogous RuIIAgIRuII trinuclear complex, ΔDΔD- and ΔDΔD-[Ag{Ru(D-Hpen-O,S)(bpy)2} 2]3+ (D-pen = D-penicillaminate), with NaI also produced mononuclear ruthenium(II) isomers with an S-bonded sulfinato group, ΔD- and ΔD-[2]+ ([Ru(D-Hpsi-O,S)(bpy)2]+ (D-psi = D- penicillaminesulfinate)), respectively, retaining the bidentate-O,S coordination mode of a D-Hpen ligand and the absolute configuration (Δ or Δ) about a RuII center. On refluxing in water, the ΔD isomer of [2]+ underwent a linkage isomerization to form ΔD-[3] + ([Ru(D-Hpsi-N,S)(bpy)2] +), in which a D-Hpsi ligand coordinates to a RuII center in a bidentate-N,S mode. Complexes [1]+,ΔD- and ΔD-[2]+, and ΔD-[3]+ were fully characterized by electronic absorption, CD, NMR, and IR spectroscopies, together with single-crystal X-ray crystallography. The electrochemical properties of these complexes, which are highly dependent on the coordination mode of sulfinate ligands, are also described.
AB - Treatment of a thiolato-bridged RuIIAgIRu II trinuclear complex, [Ag{Ru(aet)(bpy)2} 2]3+ (aet = 2-aminoethanthiolate; bpy = 2,2'-bipyridine), with NaI in aqueous ethanol under an aerobic condition afforded a mononuclear ruthenium(II) complex having an S-bonded sulfinato group, [1]+ ([Ru(aesi-N, S)(bpy)2]+ (aesi = 2-aminoethanesulfinate)). Similar treatment of optically active isomers of an analogous RuIIAgIRuII trinuclear complex, ΔDΔD- and ΔDΔD-[Ag{Ru(D-Hpen-O,S)(bpy)2} 2]3+ (D-pen = D-penicillaminate), with NaI also produced mononuclear ruthenium(II) isomers with an S-bonded sulfinato group, ΔD- and ΔD-[2]+ ([Ru(D-Hpsi-O,S)(bpy)2]+ (D-psi = D- penicillaminesulfinate)), respectively, retaining the bidentate-O,S coordination mode of a D-Hpen ligand and the absolute configuration (Δ or Δ) about a RuII center. On refluxing in water, the ΔD isomer of [2]+ underwent a linkage isomerization to form ΔD-[3] + ([Ru(D-Hpsi-N,S)(bpy)2] +), in which a D-Hpsi ligand coordinates to a RuII center in a bidentate-N,S mode. Complexes [1]+,ΔD- and ΔD-[2]+, and ΔD-[3]+ were fully characterized by electronic absorption, CD, NMR, and IR spectroscopies, together with single-crystal X-ray crystallography. The electrochemical properties of these complexes, which are highly dependent on the coordination mode of sulfinate ligands, are also described.
UR - http://www.scopus.com/inward/record.url?scp=79958138547&partnerID=8YFLogxK
U2 - 10.1021/ic102319p
DO - 10.1021/ic102319p
M3 - 学術論文
C2 - 21561071
AN - SCOPUS:79958138547
SN - 0020-1669
VL - 50
SP - 4764
EP - 4771
JO - Inorganic Chemistry
JF - Inorganic Chemistry
IS - 11
ER -