METAL ALKYL AND METAL ARYL COMPOUNDS .48. MONOMERIC, TETRAMERIC, AND POLYMERIC SODIUM FLUORENIDE.S[S = ME2N(CH2)2N(ME)(CH2)2NME2, ME2N(CH2)NNME2 (N = 2, 3)]

被引:42
作者
CORBELIN, S [1 ]
KOPF, J [1 ]
WEISS, E [1 ]
机构
[1] UNIV HAMBURG,INST ANORGAN & ANGEW CHEM,MARTIN LUTHER KING PLATZ 6,W-2000 HAMBURG 13,GERMANY
关键词
ORGANOSODIUM COMPOUNDS; FLUORENIDE CARBANIONS; SOLVATION EFFECTS;
D O I
10.1002/cber.19911241107
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
The metallation of fluorene with sodium butanide (NanBu) in the presence of N bases yields solvated sodium fluorenide. Base adducts with bi- and tridentate N-chelating ligands have been isolated: Na(fluorenide)(pmdta) (1) [PMDTA = Me2N(CH2)2N(Me)(CH2)2NMe2], [Na(fluorenide)(tmeda)]n (2) [TMEDA = Me2N(CH2)2NMe2], [Na(fluorenide)(tmpda)]4 (3) [TMPDA = Me2N(CH2)3NMe2]. According to X-ray diffraction studies monomeric (1), polymeric (2), and cyclic-tetrameric (3) structures are present in the crystal. These pronounced structural variations are explained on the basis of ionic contact aggregates where together with coulomb interactions the steric requirements of the ligands become rather important. Contact distances between Na ions and several C atoms of the carbanion may vary (ca. 260-300 pm) and definite coordination numbers become meaningless.
引用
收藏
页码:2417 / 2422
页数:6
相关论文
共 32 条
[1]   ADDUCTS OF CYCLOPENTADIENYL SODIUM AND METHYLCYCLOPENTADIENYL SODIUM WITH OXYGEN BASES AND NITROGEN BASES - STRUCTURE OF CYCLOPENTADIENYLSODIUMTETRAMETHYLETHYLENEDIAMINE, NA(C5H5)(ME2NCH2CH2NME2) [J].
AOYAGI, T ;
SHEARER, HMM ;
WADE, K ;
WHITEHEAD, G .
JOURNAL OF ORGANOMETALLIC CHEMISTRY, 1979, 175 (01) :21-31
[2]   POLYMORPHISM OF AN ORGANO-LITHIUM COMPOUND - DILITHIUM 1,2-DIPHENYLBENZOCYCLOBUTADIENEDIIDE - 2 TETRAMETHYLETHYLENEDIAMINE [J].
BOCHE, G ;
ETZRODT, H ;
MASSA, W ;
BAUM, G .
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION IN ENGLISH, 1985, 24 (10) :863-864
[3]   CRYSTAL-STRUCTURE OF THE ETA-3-ALLYLLITHIUM COMPOUND [1,3-DIPHENYLALLYLLITHIUM.DIETHYL ETHER]N [J].
BOCHE, G ;
ETZRODT, H ;
MARSCH, M ;
MASSA, W ;
BAUM, G ;
DIETRICH, H ;
MAHDI, W .
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION IN ENGLISH, 1986, 25 (01) :104-105
[4]  
BOCHE G, 1985, ANGEW CHEM, V97, P858
[5]  
BOCHE G, COMMUNICATION
[6]  
BOCHE G, 1986, ANGEW CHEM, V98, P86
[7]   PI GROUPS IN ION-PAIR BONDING - FLUORENYLLITHIUM BISQUINUCLIDINE [J].
BROOKS, JJ ;
STUCKY, GD ;
RHINE, W .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1972, 94 (21) :7339-&
[8]   ORGANIC-ANIONS .8. A SIMPLE ELECTROSTATIC MODEL FOR BENZYL-LITHIUMS AND RELATED ALKYL-LITHIUMS [J].
BUSHBY, RJ ;
TYTKO, MP .
JOURNAL OF ORGANOMETALLIC CHEMISTRY, 1984, 270 (03) :265-270
[9]   METAL-ALKYL AND METAL-ARYL COMPOUNDS .46. PHENYLSODIUM COMPOUNDS WITH ETA-3-ALLYL OR ETA-6-PHENYL COORDINATION [J].
CORBELIN, S ;
KOPF, J ;
LORENZEN, NP ;
WEISS, E .
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION IN ENGLISH, 1991, 30 (07) :825-827
[10]  
CORBELIN S, 1991, ANGEW CHEM, V103, P875