顺式-{内(外)消旋-1,2-双[烷基(芳基)亚砜]乙烷}合钯(Ⅱ)配合物的立体化学及晶体结构

Stereochemistry and Crystal Structures of Palladium (Ⅱ) Complexes with cis- {meso(race)-1, 2-bis[alkyl(aryl)sulfinyl]ethane}

本文报道了高、低熔点的RS(O)CH_2CH_2S(O)R(R=n-C_3H_7,n-C_8H_(17),C_6H_5)与钯(Ⅱ)的配合物(PdCl_2·L)的合成与性质.并对R=n-C_3H_7的一对配合物进行了单晶分析,发现高熔点配体为内消旋体,低熔点配体为外消旋体.

Six complexes of palladium ( Ⅱ ) with meso- and race-diastereoisomeric RS(O)CH2CH2-S(O)R(abbr. to meso-, race-BXSE. R = n-C3H7, C6H5, n-C8H17, X = Pr, P, O) were prepared. The crystal structures of PdCl2-meso-BPrSE ( I ) and PdCl2.race-BPrSE( Ⅱ ) were determined. Crystal data: I : P212121, a = 9. 3650(9), b=9.747(2), c=19. 341(5) A , Z=4, R=0. 044; Ⅱ: Ibca, a = 9. 442(1), 6=15. 386(4), c = 20. 095(3)A , Z=8, R=0. 030.The IR spectra indicate that the ligands are bonded to Palladium ( Ⅱ ) via sulfur atoms to form the cis-chelated complexes, which has been confirmed by the crystal Structures. △vso[vso complex -tvso ligand] for different R groups varies in the order: meso-BPrSE- race-BPrSE>meso-BOSE- race-BOSE> meso-BPSE- race-BOSE.I has a C1 symmetry and Ⅱ has C2 symmetry. The four coordinated atoms around palladium (Ⅱ ) form a right square plane for Ⅱ and a only slightly tetrahedrally distorted plane for I . It can be concluded that the higher melting point BPrSE is of meso form and the lower melting point BPrSE is of rac form.