1,3-dimethylimidazolin-2-ylidene carbene donor ligation in lanthanide silylamide complexes

被引:109
作者
Herrmann, WA
Munck, FC
Artus, GRJ
Runte, O
Anwander, R
机构
[1] UNIV STUTTGART,INST TECH CHEM 1,D-70569 STUTTGART,GERMANY
[2] TECH UNIV MUNICH,INST ANORGAN CHEM,D-85747 GARCHING,GERMANY
关键词
D O I
10.1021/om9607715
中图分类号
O61 [无机化学];
学科分类号
070301 ; 081704 ;
摘要
The synthesis and X-ray crystal structures of Y[N(SiHMe(2))(2)](3)(carbene), (carbene = 1,3-dimethylimidazolin-2-ylidene, x = 1, 2) are described. The donor capability of the strongly nucleophilic carbene ligand is expressed in both the displacement of two THF ligands by one carbene ligand in precursor compound Y[N(SiHMe(2))(2)](3)(THF)(2) and by the addition of a second carbene ligand to yield the preferred (3 + 2) trigonal bipyramidal coordination geometry. In particular, the structural data reveal that the carbene ligands affect the coordination mode of the bis(dimethylsilyl)amide counterligands by forcing them to form close beta-Si-H(silylamide)-yttrium agostic contacts. According to Pearson's terminology such carbene ligands have to be classified as hard donor ligands.
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收藏
页码:682 / 688
页数:7
相关论文
共 72 条
[21]   ORGANOLANTHANIDE HYDRIDE CHEMISTRY .1. SYNTHESIS AND X-RAY CRYSTALLOGRAPHIC CHARACTERIZATION OF DIMERIC ORGANOLANTHANIDE AND ORGANOYTTRIUM HYDRIDE COMPLEXES [J].
EVANS, WJ ;
MEADOWS, JH ;
WAYDA, AL ;
HUNTER, WE ;
ATWOOD, JL .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1982, 104 (07) :2008-2014
[22]  
FORSYTH CM, 1991, J ORGANOMETALLICS, V10, P2543
[23]   CHIRAL ORGANOLANTHANIDES DESIGNED FOR ASYMMETRIC CATALYSIS - SYNTHESIS, CHARACTERIZATION, AND CONFIGURATIONAL INTERCONVERSIONS OF CHIRAL, C-1-SYMMETRICAL ORGANOLANTHANIDE HALIDES, AMIDES, AND HYDROCARBYLS [J].
GIARDELLO, MA ;
CONTICELLO, VP ;
BRARD, L ;
SABAT, M ;
RHEINGOLD, AL ;
STERN, CL ;
MARKS, TJ .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1994, 116 (22) :10212-10240
[24]   CHIRAL ORGANOLANTHANIDES DESIGNED FOR ASYMMETRIC CATALYSIS - A KINETIC AND MECHANISTIC STUDY OF ENANTIOSELECTIVE OLEFIN HYDROAMINATION/CYCLIZATION AND HYDROGENATION BY C-1-SYMMETRICAL ME(2)SI(ME(4)C(5))(C(5)H(3)R-ASTERISK)LN COMPLEXES WHERE R-ASTERISK=CHIRAL AUXILIARY [J].
GIARDELLO, MA ;
CONTICELLO, VP ;
BRARD, L ;
GAGNE, MR ;
MARKS, TJ .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1994, 116 (22) :10241-10254
[25]   ON STABILIZING A SINGLET METHYLENE [J].
GLEITER, R ;
HOFFMANN, R .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1968, 90 (20) :5457-&
[26]  
GREENWALD AC, 1993, RARE EARTH DOPED SEM
[27]   MONO(PENTAMETHYLCYCLOPENTADIENYL) COMPLEXES OF CERIUM(III) - SYNTHESIS, MOLECULAR-STRUCTURE, THERMAL-STABILITY, AND REACTIVITY OF (C5ME5)CEX2 (X = 2,6-DI-TERT-BUTYLPHENOXO, CH(SIME3)2, AND N(SIME3)2) COMPLEXES [J].
HEERES, HJ ;
MEETSMA, A ;
TEUBEN, JH ;
ROGERS, RD .
ORGANOMETALLICS, 1989, 8 (11) :2637-2646
[28]  
Heijden H. v. d., 1989, ORGANOMETALLICS, V8, P255
[29]   MULTIPLE BONDS BETWEEN MAIN-GROUP ELEMENTS AND TRANSITION-METALS .139. NUCLEOPHILIC CYCLOCARBENES AS LIGANDS IN METAL-HALIDES AND METAL-OXIDES [J].
HERRMANN, WA ;
OFELE, K ;
ELISON, M ;
KUHN, FE ;
ROESKY, PW .
JOURNAL OF ORGANOMETALLIC CHEMISTRY, 1994, 480 (1-2) :C7-C9
[30]   METAL-COMPLEXES OF N-HETEROCYCLIC CARBENES - A NEW STRUCTURAL PRINCIPLE FOR CATALYSTS IN HOMOGENEOUS CATALYSIS [J].
HERRMANN, WA ;
ELISON, M ;
FISCHER, J ;
KOCHER, C ;
ARTUS, GRJ .
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION IN ENGLISH, 1995, 34 (21) :2371-2374