Ulrike Kilimann

Neue Cyclooctatetraenyl-lanthanid(III)-Komplexe

Zusammenfassung Five series of novel mono(cyclooctatetraenyl) lanthanide(III) complexes have been synthesized and characterized. The organolanthanides (COT)Ln (HBpz 3 ) ( 1 ), (COT)Ln[HB(3,5-Me 2 pz) 3 ] ( 2 ), (COT)Ln[CpCo{P(O)(OEt) 2 } 3 ] ( 3 ), (COT)Ln[Ph 2 P(NSiMe 3 ) 2 ] (THF) ( 4 ) and (COT)Ln[MeOC 6 H 4 C(NSiMe 3 ) 2 ](THF) ( 5 ) (Ln  Ce, Pr, Nd, Sm) are readily accessible through metathetical reactions of [(COT)Ln(μ-Cl)(THF) 2 ] 2 with the appropriate anionic ligands (COT = η 8 -cyclooctatetraenyl, Cp = η 5 - cyclopentadienyl, pz = pyrazol-1-yl).

Cyclooctatetraenyl-komplexe der frühen übergangsmetalle und lanthanoide: III. Cyclooctatetraenyl-lanthanoidtriflate und -iodide: Neue ausgangsmaterialien für die organolanthanoid-chemie

Abstract The dimeric complexes [(COT)Ln(μ-O 3 SCF 3 )(THF) 2 ] 2 (Ln  Ce ( 1 ), Pr ( 2 ), Nd ( 3 ), Sm ( 4 )) are easily prepared by treatment of anhydrous lanthanide(III) triflates with equimolar amounts of K 2 COT (COT = η 8 -cyclooctatetraenyl(2−)). The reaction of lanthanide triiodides with K 2 COT affords monomeric complexes of the type (COT)Ln(I)(THF) 3 (Ln  Nd ( 5 ), Sm ( 6 )). Due to their increased solubility in polar organic solvents these new precursors offer preparative advantages over the previously used chloro derivatives [(COT)Ln(μ-Cl)(THF) 2 ] 2 . The molecular structures of 3 and 5 have been determined by X-ray diffraction.

Viergliedrige anorganische ringsysteme des zweiwertigen zinns und bleis: Synthese und struktur von chelatstabilisierten stannylenen und plumbylenen

Abstract The synthesis of silylated tin(II) and lead(II) diiminophosphinates, [Ph 2 P(NSiMe 3 ) 2 ] 2 M ( 1 : M = Sn, 2 : M = Pb) is described. Benzamidinates of the type [RC 6 H 4 C(NSiMe 3 ) 2 ] 2 M ( 3 : R = Ph, M = Sn; 4 : R = Me, M = Pb; 5 : R = CF 3 , M = Pb) are prepared analogously. Treatment of PbCl 2 with two equivalents of Li[Me 2 Si(O t Bu)(N t Bu)] yields [Me 2 Si(O t Bu)(N t Bu)] 2 Pb ( 6 ). The molecular structures of 1 , 2 and 5 have been determined by single-crystal X-ray diffraction studies.

Cyclooctatetraenyl-komplexe der frühen übergangsmetalle und lanthanoide: IV. Strukturchemie des anionisichen sandwich-komplexes [Ce(COT)2]−☆

Abstract The cerocene(III) derivatives [Li(THF) 4 ][Ce(COT) 2 ] ( 1 ) and (THF) 3 Na(μ-COT)Ce(COT) ( 2 ) have been prepared and characterized structurally by an X-ray diffraction study (COT  η 8 -cycloocta-tetraenyl(2−)). The molecular structures differ significantly, depending on the nature of the alkali metal cation. In the solid state, compound 1 consists of separated ion pairs. In 2 a cyclooctatetraenyl ligand bridges cerium and sodium to give a linear (COT)Ce(μ-COT)Na arrangement.

Diferrocenyidichalkogenide: Synthese und struktur von Bis[2-(dimethylaminomethyl)ferrocenyl]diselenid

Abstract Oxidation of Li[CpFeC 5 H 3 (CH 2 NMC 2 )Ch] (Ch = S, Se, Te) gives the functionally substituted diferrocenyldichalcogenides [CpFeC 5 H 3 (CH 2 NMe 2 ) Ch] 2 in moderate yields. The molecular structure of [CPFeC 5 H 3 (CH 2 NMe 2 )Se] 2 has been determined by single-crystal X-ray analysis (orthorhombic, P 2 1 2 1 2 1 , a 976.7(1), b 1560.7 (1), c 1632.0 (2) pm, R = 0.023).

Lanthanides and actinides. Annual survey covering the year 1992

This review has been restricted to compounds of the lanthanides and actinides containing M-C bonds as defined by Section 29 of Chemical Abstracts. The prelanthanides SC, Y and La have been included because of their similar size and charge to the lanthanides. Abstracts of papers presented at conferences, dissertations and patents have mostly been excluded. Several general review articles on f-element organometallic compounds appeared in 1992. Ephritikhine [l] published a survey of organoactinide chemistry, focusing on work done since 1985 (184 references). Complexes with cyclopentadienyl and other dienyls (pentadienyl, cyclohexadienyl, indenyl, phospholyl), cyclooctatetraenyl and arene ligands, hydrocarbyls and hydrides and the structures and stability of some organoactinides were the subject of this review. Two annual surveys were published by R.D. Rogers and L.M. Rogers covering the years 1987-1989 (370 references) [ 23 and 1990 (102 references) [ 31. These reviews have been restricted to compounds of the lanthanides and actinides containing M-C bonds. A few more specialized review articles also appeared in 1992. Fryzuk [4] reported on ligand design in inorganic chemistry. In this article an overview is given of the strategy used to design the tridentate ligand -N(SiMe,CH,PR,),, which is suitable for coordination to both late and early transition metals. Extension of this chemistry to Group 3 (Y, La) elements and the lanthanides (Ce, Sm, Eu, Er, Yb, Lu) is also discussed (total of 38 references). Evans et al. [ 51 published a study of the reactivity of hydrazines with organometallic samarium complexes (46 references). This study shows that there is sufficient space in the coordination environment generated by two (C,Me,),Sm units to derivatize substrates inside the cavity formed by four C,Me, rings. Giardello et al. [6] reviewed organo-f-element thermochemistry. This

Ferrocenliganden in der Lanthanid-Chemie: Chelatstabilisierung des ersten Diorganyllanthanid( III)-halogenids

Abstract Dark red crystalline [(FcN) 2 Yb(μ-Cl) 2 Li(THF) 2 ] ( 2 ) has been prepared by treatment of anhydrous YbCl 3 with 2-(dimethylaminome

Cyclooctatetraenyl-komplexe der frühen Übergangsmetalle und lanthanoide: V. Synthese und struktur von monocyclooctatetraenyl-komplexen des dreiwertigen Titans

Abstract [(COT)Ti(μ-Cl)(THF)]2 (1) reacts with K[HBpz3] or K[HB(3,5-Me2pz)3] to give the new monocyclooctatetraenyl half-sandwich complexes (COT)Ti[HBpz3] (2) and (COT)Ti[HB(3,5-Me2pz)3] (3) respectively, as dark green, air-sensitive solids (COT  η8-cyclooctatetraenyl(2-)). The molecular structure of 2 has been determined by an X-ray diffraction study. The monomeric organotitanium(III) complexes (COT)Ti[PhC(NSiMe3) 2](THF) (4), (COT)Ti[MeOC6H4C(NSiMe3)2](THF) (5) and (COT)Ti[Ph2P (NSiMe3)2] (6) have been prepared by treatment of [(COT)Ti(μ-Cl)(THF)]2 (1) with the corresponding heteroallylic ligands.

Cyclooctatetraenyl-komplexe der frühen übergangsmetalle und lanthanoide: II. Neue cyclooctatetraenyl-halsandwich-komplexe des yttriums☆

Abstract Dimeric [(COT)Y(μ-O 3 SCF 3 THF)] 2 ( 1 ) is introduced as a versatile starting material for new monocyclooctatetraenyl complexes of yttrium (COT  cyclooctatetraenyl(2−)). Treatment of 1 with pyra-zolylborate anions yields the monomeric half-sandwich complexes (COT)Y(HBpz 3 ) ( 2 ) and (COT)Y[HB(3,5-Me 2 pz) 3 ] ( 3 ).The yttrium benzamidinates (COT)Y[MeOC 6 H 4 C(NSiMe 3 ) 2 ]THF ( 4 ) and (COT)Y[CF 3 C 6 H 4 C(NSiMe 3 )2](THF) ( 5 ) are prepared similarly. An yttrium phosphazene derivative, (COT)Y[Ph 2 P(NSiMe 3 ) 2 ](THF) ( 6 ) is obtained by treating 1 with Li[Ph 2 P(NSiMe 3 ) 2 ]. All new organoyttrium complexes have been fully characterized by elemental analyses and spectroscopic methods including 89 Y NMR spectroscopy.

Cyclooctatetraenyl-komplexe der frühen übergangsmetalle und lanthanoide

Abstract Dimeric [(COT)Y(μ-O 3 SCF 3 THF)] 2 ( 1 ) is introduced as a versatile starting material for new monocyclooctatetraenyl complexes of yttrium (COT  cyclooctatetraenyl(2−)). Treatment of 1 with pyra-zolylborate anions yields the monomeric half-sandwich complexes (COT)Y(HBpz 3 ) ( 2 ) and (COT)Y[HB(3,5-Me 2 pz) 3 ] ( 3 ).The yttrium benzamidinates (COT)Y[MeOC 6 H 4 C(NSiMe 3 ) 2 ]THF ( 4 ) and (COT)Y[CF 3 C 6 H 4 C(NSiMe 3 )2](THF) ( 5 ) are prepared similarly. An yttrium phosphazene derivative, (COT)Y[Ph 2 P(NSiMe 3 ) 2 ](THF) ( 6 ) is obtained by treating 1 with Li[Ph 2 P(NSiMe 3 ) 2 ]. All new organoyttrium complexes have been fully characterized by elemental analyses and spectroscopic methods including 89 Y NMR spectroscopy.