TY - JOUR
T1 - Enantiomer separation of tris(2,2'-bipyridine)ruthenium(II)
T2 - Interaction of a D3-symmetric cation with a C2-symmetric anion
AU - Puttreddy, Rakesh
AU - Hutchison, James A.
AU - Gorodetski, Yuri
AU - Harrowfield, Jack
AU - Rissanen, Kari
N1 - Publisher Copyright:
© 2015 American Chemical Society.
PY - 2015/4/1
Y1 - 2015/4/1
N2 - A compound widely used in the separation of the enantiomers of Δ,Λ-[Ru(bipy)3]2+ (bipy = 2,2'-bipyridine) and originally described as "a curious lattice compound" with the formula Δ-[Ru(bipy)3]3[Sb2(R,R-tart)2]2I2·18H2O (tart = tetradeprotonated, carboxyl and hydroxyl, tartaric acid anion) has been crystallographically characterized as this species with a slightly higher degree of hydration (19.5H2O). The crystal lattice has a layered structure in which sheets containing Δ-[Ru(bipy)3]2+ cations and iodide anions alternate with those containing [Sb2(R,R-tart)2]2- anions and water. The role of the iodide ions, which lie in pseudohexagonal cavities formed by the array of three inequivalent but very similar Δ-[Ru(bipy)3]2+ cations, all having their C3 axes directed very close to perpendicular to the sheet, appears to be to favor the orientation of the maximum number of CH units toward the [Sb2(R,R-tart)2]2- entities and to engender formation of (Δ-[Ru(bipy)3]2+)3([Sb2(R,R-tart)2]2-)2 groups optimizing the association of the D3-symmetric cations with the C2-symmetric anionic resolving agent. This may explain the known superiority of the resolution of Δ,Λ-[Ru(bipy)3]2+ with the anion mixture of I- and [Sb2(R,R-tart)2]2- over that with just [Sb2(R,R-tart)2]2- alone.
AB - A compound widely used in the separation of the enantiomers of Δ,Λ-[Ru(bipy)3]2+ (bipy = 2,2'-bipyridine) and originally described as "a curious lattice compound" with the formula Δ-[Ru(bipy)3]3[Sb2(R,R-tart)2]2I2·18H2O (tart = tetradeprotonated, carboxyl and hydroxyl, tartaric acid anion) has been crystallographically characterized as this species with a slightly higher degree of hydration (19.5H2O). The crystal lattice has a layered structure in which sheets containing Δ-[Ru(bipy)3]2+ cations and iodide anions alternate with those containing [Sb2(R,R-tart)2]2- anions and water. The role of the iodide ions, which lie in pseudohexagonal cavities formed by the array of three inequivalent but very similar Δ-[Ru(bipy)3]2+ cations, all having their C3 axes directed very close to perpendicular to the sheet, appears to be to favor the orientation of the maximum number of CH units toward the [Sb2(R,R-tart)2]2- entities and to engender formation of (Δ-[Ru(bipy)3]2+)3([Sb2(R,R-tart)2]2-)2 groups optimizing the association of the D3-symmetric cations with the C2-symmetric anionic resolving agent. This may explain the known superiority of the resolution of Δ,Λ-[Ru(bipy)3]2+ with the anion mixture of I- and [Sb2(R,R-tart)2]2- over that with just [Sb2(R,R-tart)2]2- alone.
UR - http://www.scopus.com/inward/record.url?scp=84926375541&partnerID=8YFLogxK
U2 - 10.1021/acs.cgd.5b00053
DO - 10.1021/acs.cgd.5b00053
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AN - SCOPUS:84926375541
SN - 1528-7483
VL - 15
SP - 1559
EP - 1563
JO - Crystal Growth and Design
JF - Crystal Growth and Design
IS - 4
ER -