[(Cy)Ru(LL*)Cl] and related half-sandwich compounds - two diastereomers in the same single crystal

被引:39
作者
Brunner, H [1 ]
Weber, M [1 ]
Zabel, M [1 ]
机构
[1] Univ Regensburg, Inst Anorgan Chem, D-93040 Regensburg, Germany
关键词
enantiomers; diastereomers; half-sandwich complexes; 1 : 1 diastereomer co-crystallization; molecular recognition;
D O I
10.1016/S0010-8545(03)00024-9
中图分类号
O61 [无机化学];
学科分类号
070301 ; 081704 ;
摘要
The ruthenium compound [(Cy)Ru(LL*)Cl] (1) crystallizes as a 1:1 mixture of the two diastereomers (R-Ru,S-C)-1 and (S-Ru,Sc)-1 in the same single crystal, whereas the corresponding osmium compound [(Cy)Os(LL*)Cl] (2), almost identical to 1 in the molecular parameters, crystallizes as the pure diastereomer (R-Os,S-C)-2. 1:1 diastereomer co-crystallization is traced back to a molecular recognition motif, the pair formation of fragments (Ar)MXY, in which X and Y are electronegative substituents. Thus, compounds of the type [(Ar)MXYZ], in particular (Cy)Ru derivatives, tend to form inversion pairs of enantiomers and also of diastereomers. Fifteen cases of 1:1 diastereomer co-crystallization in half-sandwich complexes are presented. The discussion is extended to [(Cy)RuLCl2] and related complexes. It is shown that there is a delicate balance between 1:1 diastereomer co-crystallization and crystallization as a pure diastereomer. (C) 2003 Elsevier B.V. All rights reserved.
引用
收藏
页码:3 / 13
页数:11
相关论文
共 41 条
[1]  
ADDADI L, 1976, ISRAEL J CHEM, V15, P116
[2]   [Ru(η6-p-cymene)Cl2(pta)] (pta=1,3,5-triaza-7-phosphatricyclo[3.3.1.1]decane):: a water soluble compound that exhibits pH dependent DNA binding providing selectivity for diseased cells [J].
Allardyce, CS ;
Dyson, PJ ;
Ellis, DJ ;
Heath, SL .
CHEMICAL COMMUNICATIONS, 2001, (15) :1396-1397
[3]   (η6-arene)ruthenium(II) complexes containing enantiomerically pure (β-aminoalkyl)phosphines or a (β-aminoalkyl) phosphinite:: synthesis, stereochemical and kinetic studies [J].
Arena, CG ;
Calamia, S ;
Faraone, F ;
Graiff, C ;
Tiripicchio, A .
JOURNAL OF THE CHEMICAL SOCIETY-DALTON TRANSACTIONS, 2000, (18) :3149-3157
[4]   Diastereoselectivity of chloride substitution reactions of cycloruthenated (R)(c)-(+)- and (S)(c)-(-)-dimethyl(1-phenylethyl)amine [J].
Attar, S ;
Catalano, VJ ;
Nelson, JH .
ORGANOMETALLICS, 1996, 15 (13) :2932-2946
[5]  
Brunner H, 1997, ENANTIOMER, V2, P133
[6]  
Brunner H, 2001, EUR J INORG CHEM, P905
[7]   Optically active transition metal complexes .107. Synthesis, properties, stereochemistry and crystal structures of diastereomeric benzene-ruthenium(II) complexes with a chiral salicylideneaminato ligand [J].
Brunner, H ;
Oeschey, R ;
Nuber, B .
JOURNAL OF THE CHEMICAL SOCIETY-DALTON TRANSACTIONS, 1996, (08) :1499-1508
[8]  
Brunner H, 1998, EUR J INORG CHEM, P1877
[9]   PROPELLER ISOMERISM OF THE TRIPHENYLPHOSPHANE LIGAND IN HALF-SANDWICH RU-II COMPLEXES [J].
BRUNNER, H ;
OESCHEY, R ;
NUBER, B .
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION IN ENGLISH, 1994, 33 (08) :866-868
[10]  
BRUNNER H, IN PRESS POLYHEDRON