TY - JOUR
T1 - Synthesis and linkage isomerization of thiolato-bridged Ru IIAgiRuII trinuclear complex with D-penicillaminate
AU - Tamura, Motoshi
AU - Yamagishi, Masakazu
AU - Kawamoto, Tatsuya
AU - Igashira-Kamiyama, Asako
AU - Tsuge, Kiyoshi
AU - Konno, Takumi
PY - 2009/9/21
Y1 - 2009/9/21
N2 - The reaction of [Ru(solvent)2(bpy)2]2+ (bpy = 2,2′-bipyridine) with D-H2pen (D-penicillamine) in ethanol/water in the presence of Ag+ gave a thiolato-bridged Ru IIAgIRuII trinuclear complex, [Ag{Ru(D-Hpen)(bpy)2}2]3+ ([1]3+), in which two octahedral [RuII(D-Hpen)(bpy)2]+ units are linked by a linear AgI ion. Of three possible isomers (ΔDΔD, ΔDΛ D, and ΛDΛD), [1]3+ formed the ΔDΔD and ΔDΔ D isomers that were separately isolated by fractional crystallization with the use of [Sb2(R,R-tartrato)2]2-. In [1]3+, each D-Hpen ligand chelates to a RuII center through thiolate and carboxylate groups, while an amine group of D-Hpen is protonated and does not participate in the coordination. On refluxing in ethanol/water, the ΔDΔD isomer of [1] 3+ was converted to ΔDΔD-[2] 3+, in which each D-Hpen ligand chelates to a RuII center through thiolate and amine groups with a non-coordinating carboxyl group. On the other hand, a similar thermal linkage isomerization was not noticed for the ΛDΛD isomer of [1]3+ under the same conditions. The isolated ΔDΔD-[1] 3+, ΛDΛD-[1]3+, and ΔD-[2]3+ were fully characterized by electronic absorption, CD, and NMR spectroscopies, along with single-crystal X-ray crystallography for ΛDΛD-[1]3+ and ΔDΔD-[2]3+.
AB - The reaction of [Ru(solvent)2(bpy)2]2+ (bpy = 2,2′-bipyridine) with D-H2pen (D-penicillamine) in ethanol/water in the presence of Ag+ gave a thiolato-bridged Ru IIAgIRuII trinuclear complex, [Ag{Ru(D-Hpen)(bpy)2}2]3+ ([1]3+), in which two octahedral [RuII(D-Hpen)(bpy)2]+ units are linked by a linear AgI ion. Of three possible isomers (ΔDΔD, ΔDΛ D, and ΛDΛD), [1]3+ formed the ΔDΔD and ΔDΔ D isomers that were separately isolated by fractional crystallization with the use of [Sb2(R,R-tartrato)2]2-. In [1]3+, each D-Hpen ligand chelates to a RuII center through thiolate and carboxylate groups, while an amine group of D-Hpen is protonated and does not participate in the coordination. On refluxing in ethanol/water, the ΔDΔD isomer of [1] 3+ was converted to ΔDΔD-[2] 3+, in which each D-Hpen ligand chelates to a RuII center through thiolate and amine groups with a non-coordinating carboxyl group. On the other hand, a similar thermal linkage isomerization was not noticed for the ΛDΛD isomer of [1]3+ under the same conditions. The isolated ΔDΔD-[1] 3+, ΛDΛD-[1]3+, and ΔD-[2]3+ were fully characterized by electronic absorption, CD, and NMR spectroscopies, along with single-crystal X-ray crystallography for ΛDΛD-[1]3+ and ΔDΔD-[2]3+.
UR - http://www.scopus.com/inward/record.url?scp=70349312652&partnerID=8YFLogxK
U2 - 10.1021/ic901181x
DO - 10.1021/ic901181x
M3 - 学術論文
C2 - 19689105
AN - SCOPUS:70349312652
SN - 0020-1669
VL - 48
SP - 8998
EP - 9004
JO - Inorganic Chemistry
JF - Inorganic Chemistry
IS - 18
ER -