102808-71-9Relevant academic research and scientific papers
Resolutions involving metal complexation. Synthesis and resolution of (±)-(2-mercaptoethyl)methylphenylarsine. Crystal and molecular structure of (-)589-[Pd{(R)-CH3CH(1-C10H 6)NMe2-C2,N}{(S)-PhMeAsCH2CH 2S-As,μ-S}PdCl{(R)-CH3CH(1-C10H ...
Leung, Pak Hing,McLaughlin, George M.,Martin, John W. L.,Wild, S. Bruce
, p. 3392 - 3395 (2008/10/08)
Full title: Resolutions involving metal complexation. Synthesis and resolution of (±)-(2-mercaptoethyl)methylphenylarsine. Crystal and molecular structure of (-)589-[Pd{(R)-CH3CH(1-C10H 6)NMe2-C2,N}{(S)-PhMeAsCH2CH 2S-As,μ-S}PdCl{(R)-CH3CH(1-C10H 6)NMe2-C2,N}]·0.67CH2Cl 2. The asymmetric chelating agent (±)-(2-mercaptoethyl)methylphenylarsine has been resolved into its optical antipodes by the fractional crystallization of unusual μ-thiolato epimers containing two ortho-metalated [(R)-[1-(dimethylamino)ethyl]-naphthyl-C2,N]palladium(II) resolving units per bridging (methylphenylarsino)ethane-2-thiolato ligand. The least soluble epimer with [α]D -283° (CH2Cl2) crystallizes in the space group P212121, with a = 10.080 (2) A?, b = 14.157 (2) A?, c = 27.918 (4) A?, and Z = 4. The structure was solved by heavy-atom methods and refined by least-squares analysis to an R of 0.052 and Rw of 0.056 for 2347 reflections. The bridging thiolato atom and the coordinated arsenic atom both have the S absolute configuration in the dinuclear complex. Treatment of the dimer with diamino-1,2-ethane removes the terminal resolving unit and affords crystalline monomeric (-)589-[(R)-1-[1-(dimethylamino)ethyl]naphthyl-C 2,N][(S)-(methylphenylarsino)ethanethiolato-As,S]-palladium(II) from which optically pure (R)-(-)589-(2-mercaptoethyl)methylphenylarsine with [α]D -16.7° (CH2Cl2) was liberated by treatment with cyanide. The (S)-(+)589 enantiomer of the ligand was obtained in a state of 72% optical purity from the residual mixture of epimeric complexes and was subsequently brought to purity by fractional crystallization of the corresponding enantiomorphic dinuclear complexes containing (S)-dimethyl(1-(α-naphthyl)ethyl)amine.
