pH-switchable inversion of the metal-centered chirality of metallabenzenes: opposite stereodynamics in reactions of ruthenabenzene with L- and D-cysteine.
We report herein the first study on the chemical interaction between metallabenzenes and bioactive molecules. Due to its unique stereoelectronic activities, a phenanthroline-derived ruthenabenzene [Ru{CHC(PPh(3))CHC(PPh(3))CH}Cl(C(12)H(8)N(2))(PPh(3))]Cl(2) (1) selectively binds cysteine in aqueous solution at physiological pH and then undergoes a dynamic inversion of configuration at the Ru center. The structure of the L-cysteine-binding product of 1 has been determined by means of X-ray diffraction. The replacement of the L-cysteine with the D form results in an inverted stereodynamic effect. Furthermore, the inversion process of the Ru-centered configuration could be conveniently controlled by a simple pH adjustment. This is attributed to the significant influence of a special intramolecular electrostatic interaction on the dynamic epimerization process of the cysteine-binding product.
State Key Laboratory for Physical Chemistry of Solid Surfaces, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005, P.R. China.
Ran
R
Lin
Hong
H
Zhang
Shunhua
S
Li
Leiqi
L
Chen
Weiguang
W
Zhang
Ting Bin
TB
Wen
Hui
H
Zhang
Haiping
H
Xia
D001555:Benzene Derivatives / Q000737:chemistry*; D018360:Crystallography, X-Ray; D003545:Cysteine / Q000031:analogs & derivatives* / Q000737:chemistry*; D006863:Hydrogen-Ion Concentration; D009682:Magnetic Resonance Spectroscopy; D008968:Molecular Conformation; D015394:Molecular Structure; D009942:Organometallic Compounds / Q000737:chemistry*; D010618:Phenanthrolines / Q000737:chemistry*; D012428:Ruthenium / Q000737:chemistry*; D013237:Stereoisomerism
D001555:Benzene Derivatives; D009942:Organometallic Compounds; D010618:Phenanthrolines; D012428:Ruthenium; D003545:Cysteine