SYNTHESIS AND MOLECULAR-STRUCTURE OF OPTICALLY-ACTIVE OXAZOLIDINE COMPLEXES OF PLATINUM(II) AND PALLADIUM(II)

被引:14
作者
ALBINATI, A
LIANZA, F
BERGER, H
ARZ, C
PREGOSIN, PS
机构
[1] SWISS FED INST TECHNOL, ANORGAN CHEM LAB, CH-8092 ZURICH, SWITZERLAND
[2] UNIV MILANO, IST CHIM FARMACEUT, I-20131 MILAN, ITALY
关键词
D O I
10.1016/S0020-1693(00)92422-8
中图分类号
O61 [无机化学];
学科分类号
070301 ; 081704 ;
摘要
Two series of optically active complexes of the type trans-PtCl2(C2H4)(oxazolidine) (3) and trans-PdCl2(PPh3)(Oxazolidine) (4), oxazolidine=NHCH(p-ClC6H4)OCH2CHR (R=a, Me; b, Et; c, Bu(i); d, Bz; e, Ph) have been prepared and characterized. The synthesis involves metal promoted cyclization of the optically active Schiff's bases p-ClC6H4CH=NCH(R)CH2OH and proceeds for both metal centers in high chemical and optical yield (diastereomeric excesses of 78-96%). Attack of the oxygen at the imine carbon results in preferential formation of complexed five-membered rings which have the cis-geometry with respect to the C-2 and C-5 substituents. The solid-state structures for 3b and 4c have been determined by X-ray diffraction. Both structures reveal expected coordination spheres with the MCl2 (C2H4 or PPh3) fragment occupying a pseudo trans position with respect to the oxazolidine C-2, C-5 substituents. This observation, combined with solution 2-D NOESY measurements, is used to rationalize the observed diastereomeric excesses. Crystallographic data for the complexes are as follows: 3b, orthorhombic, space group P2(1)2(1)2(1), a=7.003(1), b=16.573(1), c=29.088(4) angstrom, V=3376.1(7) angstrom3, Z=8; 4c, orthorhombic space group P2(1)2(1)2(1), a=11.921(2), b=12.241(1), c=21.107(2) angstrom, V=3080(1) angstrom3, Z=4. The structures have been refined to R factors of 0.04 and 0.05, respectively.
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页码:771 / 780
页数:10
相关论文
共 30 条
[1]   2D NOESY OF PALLADIUM PI-ALLYL COMPLEXES - REPORTER LIGANDS, COMPLEX DYNAMICS, AND THE X-RAY STRUCTURE OF [PD(ETA-3-C4H7)(BPY)](CF3SO3) (BPY = BIPYRIDINE) [J].
ALBINATI, A ;
KUNZ, RW ;
AMMANN, CJ ;
PREGOSIN, PS .
ORGANOMETALLICS, 1991, 10 (06) :1800-1806
[2]   PREPARATIVE AND H-1-NMR SPECTROSCOPIC STUDIES ON PALLADIUM(II) AND PLATINUM(II) QUINOLINE-8-CARBALDEHYDE (1) COMPLEXES - X-RAY STRUCTURES OF THE CYCLOMETALATED ACYL COMPLEX PDCL(C(O)C9H6N)(PPH3).PPH3 AND TRANS-PTCL2(1)(PET3) [J].
ALBINATI, A ;
ANKLIN, CG ;
GANAZZOLI, F ;
RUEGG, H ;
PREGOSIN, PS .
INORGANIC CHEMISTRY, 1987, 26 (04) :503-508
[3]   ASYMMETRIC-SYNTHESIS OF COMPLEXED CYCLIC N,O-ACETALS BY USE OF PLATINUM(II) COMPLEXES - CRYSTAL-STRUCTURE OF TRANS-[PTCL2(C2H4)(2-PARA-NO2C6H4(CHNH(CH2)3O-))] [J].
ALBINATI, A ;
ARZ, C ;
PREGOSIN, PS .
JOURNAL OF ORGANOMETALLIC CHEMISTRY, 1989, 371 (01) :C18-C20
[4]   SYNTHESIS AND X-RAY STRUCTURE OF REACTIVE ALPHA-AMINO ETHERS STABILIZED VIA METAL COMPLEXATION [J].
ALBINATI, A ;
ARZ, C ;
PREGOSIN, PS .
INORGANIC CHEMISTRY, 1988, 27 (12) :2015-2016
[5]   NJ(PT,H) AND PT-LESS-THAN-H-C INTERACTIONS IN SCHIFF-BASE COMPLEXES OF 2-(BENZYLIDENEAMINO)-3-METHYLPYRIDINE - MOLECULAR-STRUCTURES OF DICHLORO(2-((2,4,6-TRIMETHYLBENZYLIDENE)AMINO)-3-METHYLPYRIDINE)(TRIETHYLARSINE)PLATINUM(II) AND DICHLORO(2-AMINO-3-METHYLPYRIDINE)(TRIETHYLPHOSPHINE)PALLADIUM(II) [J].
ALBINATI, A ;
ARZ, C ;
PREGOSIN, PS .
INORGANIC CHEMISTRY, 1987, 26 (04) :508-513
[6]   APPLICATIONS OF P-31 2-D EXCHANGE NMR-SPECTROSCOPY TO PLATINUM CHEMISTRY [J].
AMMANN, C ;
PREGOSIN, PS ;
SCRIVANTI, A .
INORGANICA CHIMICA ACTA, 1989, 155 (02) :217-220
[7]  
[Anonymous], 1974, INT TABLES XRAY CRYS, VIV
[8]   TRANS-INFLUENCE - ITS MEASUREMENT AND SIGNIFICANCE [J].
APPLETON, TG ;
CLARK, HC ;
MANZER, LE .
COORDINATION CHEMISTRY REVIEWS, 1973, 10 (3-4) :335-422
[9]  
ARSENIYADIS S, 1990, HETEROCYCLES, V31, P1789
[10]   CRYSTAL AND MOLECULAR-STRUCTURE OF TRANS-DICHLOROBIS(OXAZOLE)PALLADIUM(II) [J].
BINAMIRASORIAGA, E ;
LUNDEEN, M ;
SEFF, K .
JOURNAL OF CRYSTAL AND MOLECULAR STRUCTURE, 1979, 9 (02) :67-75