ORGANOMETALLIC COMPOUNDS OF THE LANTHANIDES .97. SYNTHESIS AND CRYSTAL-STRUCTURES OF MONOMERIC BIS(ETHYLTETRAMETHYLCYCLOPENTADIENYL) AMIDE AND ALKYL DERIVATIVES OF THE LANTHANIDES

被引：35
作者：
SCHUMANN, H [1 ]
ROSENTHAL, ECE [1 ]
KOCIOKKOHN, G [1 ]
MOLANDER, GA [1 ]
WINTERFELD, J [1 ]
机构：
[1] UNIV COLORADO,DEPT CHEM & BIOCHEM,BOULDER,CO 80309
来源：
JOURNAL OF ORGANOMETALLIC CHEMISTRY | 1995年 / 496卷 / 02期
基金：
美国国家卫生研究院;
关键词：
YTTRIUM; NEODYMIUM; SAMARIUM; LUTETIUM; AMIDES; CRYSTAL STRUCTURE;
D O I：
10.1016/0022-328X(95)05496-C
中图分类号：
O61 [无机化学];
学科分类号：
070301 ; 081704 ;
摘要：
The trichlorides of yttrium, neodymium, samarium and lutetium react with 2 equiv. of Na[C(5)Me(4)Et] in THF to form [(C(5)Me(4)Et)(2)LnCl(THF)] (Ln = Y, 1; Nd, 2; Sm, 3; Lu, 4). Metathesis of 1-4 with NaN(SiMe(3))(2) and LiCH(SiMe(3))(2) in toluene gives [(C(5)Me(4)Et)(2)Ln{E(SiMe(3))(2)}] (E = N, Ln = Y, 5; Nd, 6; Sm, 7; Lu, 8; E = CH, Ln = Y, 9; Nd, 10; Sm, 11). The new compounds were characterized by elemental analysis and mass and NMR spectrometry. Additionally, X-ray structural analysis of 5 and 11 was performed. The silylamide 5 crystallized in the monoclinic space group C2/c with a = 9.169(2), b = 21.166(8), c = 15.625(3) Angstrom, beta = 94.15(2)degrees, V = 3025(2) Angstrom(3) and Z = 4. The final refinement resulted in R(1) = 2.86% (I > 4 sigma(I)). Compound 11 crystallized in the orthorhombic space group Pbca with a = 18.499(6), b = 14.181(6), c = 23.290(5) Angstrom, V = 6110(3) Angstrom(3), Z = 8, and R(1) = 3.04% (I > 4 sigma(I)).
引用
收藏
页码：233 / 240
页数：8
相关论文
共 41 条
[1]   CHIRAL ORGANOLANTHANIDE COMPLEXES FOR ENANTIOSELECTIVE OLEFIN HYDROGENATION [J].
CONTICELLO, VP ;
BRARD, L ;
GIARDELLO, MA ;
TSUJI, Y ;
SABAT, M ;
STERN, CL ;
MARKS, TJ .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1992, 114 (07) :2761-2762
[2]   AN IMPROVED SYNTHESIS OF BIS(TRIMETHYLSILYL)CHLOROMETHANE [J].
COWLEY, AH ;
KEMP, RA .
SYNTHESIS AND REACTIVITY IN INORGANIC AND METAL-ORGANIC CHEMISTRY, 1981, 11 (06) :591-595
[3]   SUB-VALENT GROUP 4B METAL ALKYLS AND AMIDES .1. SYNTHESIS AND PHYSICAL-PROPERTIES OF KINETICALLY STABLE BIS[BIS(TRIMETHYSILYL)METHYL]-GERMANIUM(II), BIS[BIS(TRIMETHYSILYL)METHYL]-TIN(II), AND BIS[BIS(TRIMETHSILYL)METHYL]-LEAD(II) [J].
DAVIDSON, PJ ;
HARRIS, DH ;
LAPPERT, MF .
JOURNAL OF THE CHEMICAL SOCIETY-DALTON TRANSACTIONS, 1976, (21) :2268-2274
[4]   REACTIONS OF YTTRIUM CARBON BONDS WITH ACTIVE HYDROGEN-CONTAINING MOLECULES - A USEFUL SYNTHETIC METHOD FOR PERMETHYLYTTROCENE DERIVATIVES [J].
DENHAAN, KH ;
WIELSTRA, Y ;
TEUBEN, JH .
ORGANOMETALLICS, 1987, 6 (10) :2053-2060
[5]   SYNTHESIS OF MONOMERIC PERMETHYLYTTROCENE DERIVATIVES - THE CRYSTAL-STRUCTURES OF ETA-5-C5H5YN(SIME3)2 AND ETA-5-C5H5YCH(SIME3)2 [J].
DENHAAN, KH ;
DEBOER, JL ;
TEUBEN, JH ;
SPEK, AL ;
KOJICPRODIC, B ;
HAYS, GR ;
HUIS, R .
ORGANOMETALLICS, 1986, 5 (08) :1726-1733
[6]  
EVANS WJ, 1993, ORGANOMETALLICS, V12, P1618
[7]   ORGANOLANTHANIDE-CENTERED HYDROAMINATION CYCLIZATION OF AMINOOLEFINS - EXPEDIENT OXIDATIVE ACCESS TO CATALYTIC CYCLES [J].
GAGNE, MR ;
NOLAN, SP ;
MARKS, TJ .
ORGANOMETALLICS, 1990, 9 (06) :1716-1718
[8]   STEREOSELECTION EFFECTS IN THE CATALYTIC HYDROAMINATION CYCLIZATION OF AMINOOLEFINS AT CHIRAL ORGANOLANTHANIDE CENTERS [J].
GAGNE, MR ;
BRARD, L ;
CONTICELLO, VP ;
GIARDELLO, MA ;
STERN, CL ;
MARKS, TJ .
ORGANOMETALLICS, 1992, 11 (06) :2003-2005
[9]   ORGANOLANTHANIDE-CATALYZED HYDROAMINATION - FACILE, REGIOSPECIFIC CYCLIZATION OF UNPROTECTED AMINO OLEFINS [J].
GAGNE, MR ;
MARKS, TJ .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1989, 111 (11) :4108-4109
[10]   ORGANOLANTHANIDE-CATALYZED HYDROAMINATION - A KINETIC, MECHANISTIC, AND DIASTEREOSELECTIVITY STUDY OF THE CYCLIZATION OF N-UNPROTECTED AMINO OLEFINS [J].
GAGNE, MR ;
STERN, CL ;
MARKS, TJ .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1992, 114 (01) :275-294
12345