STEREOCHEMICAL VARIABILITY IN SAMARIUM(II) REAGENTS USING CARBAZOLE AS AN ALTERNATIVE TO IODIDE - SYNTHESIS AND STRUCTURE OF CIS-(C12H8N)2SM(THF)4 AND TRANS-(C12H8N)2SM(N-MEIM)4

被引:50
作者
EVANS, WJ
RABE, GW
ZILLER, JW
机构
[1] Department of Chemistry, University of California, Irvine
关键词
D O I
10.1021/om00017a022
中图分类号
O61 [无机化学];
学科分类号
070301 ; 081704 ;
摘要
SMI2(THF)2 reacts with potassium carbazole (KC12H8N, KCbz) in a 1:2 ratio at room temperature in THF to form (C12H8N)2SM(THF)4, 1.1 reacts with N-methylimidazole (N-MeIm) in a 1:4 ratio at room temperature in THF to form (C12H8N)2SM(N-MeIM)4, 2. X-ray crystallographic studies on 1 and 2 show that both have distorted octahedral structures but that (Cbz)2SM(THF)4 crystallizes as the cis isomer (N-Sm-N: 109.8(1)-degrees) and (Cbz)2SM(N-Melm)4 crystallizes as the trans isomer (N(Cbz)-Sm-N(Cbz)): 151.7(3) and 159.2(5)-degrees). 1 crystallizes from hot THF in space group P1BAR [C(1/i); No. 2] with unit cell parameters at 173 K of a = 9.8862(9) angstrom, b = 10.3285(7) angstrom, c = 18.3670(16) angstrom, alpha = 100.368(6)-degrees, beta = 98.522(7)-degrees, gamma = 102.898(6)-degrees, V = 1763.2(3) angstrom3, and Z = 2 with D(calcd) = 1.45 g cm-3. Least-squares refinement of the model based on 7577 observed reflections (\F(o)\ > 3.0sigma(\F(o)\)) converged to a final R(F) = 3.0%. 2 crystallized from THF/benzene in space group P3BAR with unit cell parameters at 163 K of a = 26.759(2) angstrom, c = 27.796(4) angstrom, V = 17 236(3) angstrom3, and Z = 18 with D(calcd) = 1.443 g CM-3. Least-squares refinement of the model based on 5505 observed reflections (\F(o)\ > 3.0sigma([F(o)\)) converged to a final R(F) = 6.5 %. The average Sm-N(Cbz) distances in 1 and 2 are 2.565(13) and 2.591(3) angstrom, respectively. The average Sm-O(THF) distance in 1 is 2.582(7) angstrom; the average Sm-N(N-MeIm) distance in 2 is 2.685(14) angstrom.
引用
收藏
页码:1641 / 1645
页数:5
相关论文
共 42 条
[11]   DIRECT APPROACHES TO ZINC POLYCHALCOGENIDE CHEMISTRY - ZNS6(N-MEIM)2 AND ZNSE4(N-MEIM)2 [J].
DEV, S ;
RAMLI, E ;
RAUCHFUSS, TB ;
STERN, CL .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1990, 112 (17) :6385-6386
[12]   SYNTHESIS AND STRUCTURE OF [M(N-METHYLIMIDAZOLE)6]S8 (M = MN, FE, NI, MG) - POLYSULFIDE SALTS PREPARED BY THE REACTION N-METHYLIMIDAZOLE + METAL-POWDER + SULFUR [J].
DEV, S ;
RAMLI, E ;
RAUCHFUSS, TB ;
WILSON, SR .
INORGANIC CHEMISTRY, 1991, 30 (11) :2514-2519
[13]   STRUCTURAL TRENDS IN BIS(PENTAMETHYLCYCLOPENTADIENYL)LANTHANIDE AND YTTRIUM COMPLEXES [J].
EVANS, WJ ;
FOSTER, SE .
JOURNAL OF ORGANOMETALLIC CHEMISTRY, 1992, 433 (1-2) :79-94
[14]   SYNTHESIS AND X-RAY CRYSTAL-STRUCTURE OF THE DIVALENT [BIS(TRIMETHYLSILYL)AMIDO]SAMARIUM COMPLEXES [(ME3SI)2N]2SM(THF)2 AND ([ME3SI)2N]SM(MU-I)(DME)(THF))2 [J].
EVANS, WJ ;
DRUMMOND, DK ;
ZHANG, HM ;
ATWOOD, JL .
INORGANIC CHEMISTRY, 1988, 27 (03) :575-579
[15]   INVESTIGATION OF ORGANOLANTHANIDE-BASED CARBON-CARBON BOND FORMATION - SYNTHESIS, STRUCTURE, AND COUPLING REACTIVITY OF ORGANOLANTHANIDE ALKYNIDE COMPLEXES, INCLUDING THE UNUSUAL STRUCTURES OF THE TRIENEDIYL COMPLEX [(C5ME5)2SM]2[MU-ETA(2)-ETA(2)-PH(CH2)2C=C=C=C-(CH2)2PH] AND THE UNSOLVATED ALKYNIDE [(C5ME5)2SM(CCCME3)]2 [J].
EVANS, WJ ;
KEYER, RA ;
ZILLER, JW .
ORGANOMETALLICS, 1993, 12 (07) :2618-2633
[16]   REACTIVITY OF TRIMETHYLALUMINUM WITH (C5ME5)2SM(THF)2 - SYNTHESIS, STRUCTURE, AND REACTIVITY OF THE SAMARIUM METHYL COMPLEXES (C5ME5)2SM[MU-ME)ALME2(MU-ME)]2SM(C5ME5)2 AND (C5ME5)2SMME(THF) [J].
EVANS, WJ ;
CHAMBERLAIN, LR ;
ULIBARRI, TA ;
ZILLER, JW .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1988, 110 (19) :6423-6432
[17]   SOLUTION SYNTHESIS AND CRYSTALLOGRAPHIC CHARACTERIZATION OF THE DIVALENT ORGANOSAMARIUM COMPLEXES (C5ME5)2SM(THF)2 AND [(C5ME5)SM(MU-I)(THF)2]2 [J].
EVANS, WJ ;
GRATE, JW ;
CHOI, HW ;
BLOOM, I ;
HUNTER, WE ;
ATWOOD, JL .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1985, 107 (04) :941-946
[18]   PARAMAGNETISM IN ORGANOLANTHANIDE COMPLEXES [J].
EVANS, WJ ;
HOZBOR, MA .
JOURNAL OF ORGANOMETALLIC CHEMISTRY, 1987, 326 (03) :299-306
[19]   SYNTHESIS AND STRUCTURE OF MONO-THF SOLVATES OF BIS(CYCLOPENTADIENYL)SAMARIUM(II) COMPLEXES - (C5ME5)2SM(THF) AND [C5H2(SIME3)3][C5H3(SIME3)2]SM(THF) [J].
EVANS, WJ ;
KOCIOKKOHN, G ;
FOSTER, SE ;
ZILLER, JW ;
DOEDENS, RJ .
JOURNAL OF ORGANOMETALLIC CHEMISTRY, 1993, 444 (1-2) :61-66
[20]  
EVANS WJ, UNPUB