Jürgen Dahlhaus

(Dimethylaminoethyl)cyclopentadienyl ligands in compounds of s- and p-block elements

The chemistry of (dimethylaminoethyl)cyclopentadienyl-substituted compounds containing s- and p-block elements is reviewed. A survey of the syntheses, properties and structures of these compounds, classified according to the group numbers in the Periodic Table, is presented. Some comments on NMR spectroscopic aspects are presented together with a discussion of solid-state structures.

Intramolekulare Basenkoordination je nach Bedarf: Der 1-(Dimethylaminoethyl)-2,3,4,5-tetramethylcyclopentadienyl-Ligand in der Komplexchemie von s-, p-, d- und f-Block-Elementen

The synthesis of cyclopentadienyl complexes containing the polydentate C5Me4(CH2CH2NMe2) ligand is described. The compounds (C5Me4CH2CH2NMe2)2M (M  Ca, Sm), (C5Me4CH2CH2 NMe2)AIEt2, [(C5Me4CH2CH2NMe2)M(CO)2]2 (M  Mo, Fe) and [(C5Me4CH2CH2NMe2)Fe(CO)2]+BF4± are obtained by standard procedures. Except for the dimeric metal carbonyls, all cyclopentadienyl compounds are characterized by an additional intramolecular coordination of the nitrogen atom in the side chain.

Zur synthese von Silicium-, Zinn- und Thallium-verbindungen mit dimethylaminoethyl-substituierten cyclopentadienyl-liganden

Abstract The dimenthylaminoethyl-functionalized cyclopentadienes 1a and 1b react with thallium ethoxide to give the air-sensitive thallium derivatives 2a and 2b . The (cyclopentadienyl)trimethylsilanes 3a and 3b and -stannanes 4a and 4b are obtained in the reaction of deprotonated 1a and 1b with Me 3 SiCl and Me 3 SnBr, respectively. The new compounds are potential Cp-transfer reagents for the synthesis of other cyclopentadienyl complexes.

(Dimethylaminoethyl)cyclopentadienyl-liganden in der chemie von gruppe-13-elementen (Al, Ga, In

Abstract The synthesis of cyclopentadienyl complexes containing polydentate C 5 R 4 (CH 2 CH 2 NMe 2 ) ligands (R  H, Me) and Group 13 elements (Al, Ga, In) is described. The compounds (C 5 Me 4 CH 2 CH 2 NMe 2 ) AlX 2 (X  Me, Cl, Br, I), (C 5 Me 4 CH 2 CH 2 NMe 2 )MCl 2 (M  Ga, In), (C 5 H 4 CH 2 CH 2 NMe 2 )AlX 2 (X  H, Me, Et, Cl), (C 5 H 4 CH 2- CH 2 NMe 2 )GaCl 2 ,and (C 5 H 4 CH 2 CH 2 NMe 2 )InMe 2 are obtained by three different procedures. All compounds that have been characterized, so far, by X-ray diffraction studies show an additional intramolecular coordination of the nitrogen atom in the side chain. Monomeric structures and sufficient volatilities make them potential candidates for MOCVD processes.

Einige Reaktionen an der Eisen—Eien—Bindung im Tetracarbonyl(1,1′,3, 3′-tetra-tert-butyl-5,5′-pentafulvalen) dieisen

Abstract Reactions of tetracarbonyl (1,1′,3,3′-tetra-tert-butyl-5,5′-pentafulvalene) diiron ( 1 ) with the halides bromine and iodine, and with the reagent HCI/O 2 , respectively, lead under cleavage of the ironiron bond to the fulvalene-bridged dinuclear dicarbonl-halide complexes (π 5 :π 5 - t Bu 4 C 10 H 4 )(CO) 4 Fe 2 X 2 , with X = Br ( 2 ), I ( 3 ), and CI ( 4 ). By reaction of 3 with the nucleophiles CH 3 Mgl, C 6 H 5 CH 2 MgBr and C 5 H 5 Na, compounds of the type ((π 5 - t Bu 4 C 10 H 4 )(CO) 4 Fe 2 R 2 with R = CH 3 ( 5 ), CH 2 C 6 H 5 ( 6 ), a C 5 H 7 ( 7 ) are formed. Treatment of 1 with potassium graphite, C 8 K, yields the dipotassium diferrate 8 . Reactions of 8 with AsBr 3 , and SbBr 3 , respectively, lead to themetal complexes (π 5 :π 5 - t Bu 4 C 10 H 4 )(CO) 4 Fe 2 (ElBr 2 ) 2 , with El = As ( 9 ), and Sb ( 10 ). It can be asumed that in all derivatives of 1 a cisoid orientation of the iron centers is maintained.

Organometallic Compounds with Bridged or (Dimethylaminoethyl)-Substituted Cyclopentadienyl Ligands

Abstract We report here the synthesis and structure of organometallic compounds with bridged or dimethylaminoethyl-substituted cyclopentadienyl ligands. A short survey of p- and d-block complexes with pentafulvalenediyl or silicon-linked cyclopentadienyl systems is followed by a discussion of cyclopentadienyl compounds containing the bi(poly)dentate ligands C5R4CH2CH2NMe2 (R=H, Me) and s- or p-block elements. Compounds of the type (C5R4CH2CH2NMe2)M (M=Li, K, Tl), (C5R4CH2CH2NMe2)2Ca, (C5R4CH2CH2NMe2)EIMe3 (El=Si, Sn), and (C5R4CH2CH2NMe2)MX2 (M=Al, Ga, In; X=H, Me, Et, Cl, Br, I) have been obtained. Those with group 2 and group 13 elements as central atoms show an intramolecular coordination of the nitrogen atom and monomeric structures; sufficient volatilities make them potential candidates for MOCVD-processes.