Nanoscale Organolanthanum Clusters: Nuclearity-Directing Role of Cyclopentadienyl and Halogenido Ligands.

Tetramethylaluminato/halogenido(X) ligand exchange reactions in half-sandwich complexes [CpR La(AlMe4 )2 ] are feasible in non-coordinating solvents and provide access to large coordination clusters of the type [CpR LaX2 ]x . Incomplete exchange reactions generate the hexalanthanum clusters [CpR 6 La6 X8 (AlMe4 )4 ] (CpR =Cp*=C5 Me5 , X=I; CpR =Cp'=C5 H4 SiMe3 , X=Br, I). Treatment of [Cp*La(AlMe4 )2 ] with two equivalents Me3 SiI gave the nonalanthanum cluster [Cp*LaI2 ]9 , while the exhaustive reaction of [Cp'La(AlMe4 )2 ] with the halogenido transfer reagents Me3 GeX and Me3 SiX (X=I, Br, Cl) produced a series of monocyclopentadienyl rare-earth-metal clusters with distinct nuclearity. Depending on the halogenido ion size the homometallic clusters [Cp'LaCl2 ]10 and [Cp'LaX2 ]12 (X=Br, I) could be isolated, whereas different crystallization techniques led to the aggregation of clusters of distinct structural motifs, including the desilylated cyclopentadienyl-bridged cluster [(µ-Cp)2 Cp'8 La8 I14 ] and the heteroaluminato derivative [Cp'10 La10 Br18 (AlBr2 Me2 )2 ]. The use of the Cp' ancillary ligand facilitates cluster characterization by means of NMR spectroscopy.

Yttrium Siloxide Complexes Bearing Terminal Methyl Ligands: Molecular Models for Ln-CH3 Terminated Silica Surfaces.

Surface organometallic chemistry (SOMC) on silica materials is a prominent approach for the generation of highly active heterogenized polymerization catalysts. Despite advanced methods of characterization, the elucidation of the catalytically active surface species remains a challenging task. Alkylated rare-earth metal siloxide complexes can be regarded as molecular models of respective covalently bonded alkylated surface species, primarily used for 1,3-diene polymerization. Here, we performed both salt metathesis reactions of [Y(MMe4 )3 ] (M = Al, Ga) with [K{OSi(OtBu)3 }] and alkylation reactions of [Y{OSi(OtBu)3 }3 ]2 with AlMe3 . The obtained complexes [Y(CH3 )[(AlMe2 ){OSi(OtBu)3 }2 ](AlMe4 )]2 , [Y(CH3 )[(AlMe2 ){OSi(OtBu)3 }2 ]-{OSi(OtBu)3 }], [Y{OSi(OtBu)3 }3 (µ-Me)Y(µ-Me)2 Y{OSi(OtBu)3 }2 (AlMe4 )], and [Y(CH3 )(GaMe4 ){OSi(OtBu)3 }]2 represent rare examples of organoyttrium species with terminal methyl groups. The formation and purity of the mixed methyl/siloxy yttrium complexes could be enhanced by treating [Y(MMe4 )3 ] with [K(MMe2 ){OSi(OtBu)3 }2 ]n (M=Al: n=2; M=Ga: n=∞). Complexes [K(MMe2 ){OSi(OtBu)3 }2 ]n were obtained by addition of [K{OSi(OtBu)3 }] to [Me2 M{OSi(OtBu)3 }]2 . Deeper insight into the fluxional behavior of the mixed methyl/siloxy yttrium complexes in solution was gained by (1) H and (13) C NMR spectroscopic studies at variable temperature and (1) H-(89) Y HSQC NMR spectroscopy.

Synthesis and stability of homoleptic metal(III) tetramethylaluminates.

Whereas a number of homoleptic metal(III) tetramethylaluminates M(AlMe(4))(3) of the rare earth metals have proven accessible, the stability of these compounds varies strongly among the metals, with some even escaping preparation altogether. The differences in stability may seem puzzling given that this class of metals usually is considered to be relatively uniform with respect to properties. On the basis of quantum chemically obtained relative energies and atomic and molecular descriptors of homoleptic tris(tetramethylaluminate) and related compounds of rare earth metals, transition metals, p-block metals, and actinides, multivariate modeling has identified the importance of ionic metal-methylaluminate bonding and small steric repulsion between the methylaluminate ligands for obtaining stable homoleptic compounds. Low electronegativity and a sufficiently large ionic radius are thus essential properties for the central metal atom. Whereas scandium and many transition metals are too small and too electronegative for this task, all lanthanides and actinides covered in this study are predicted to give homoleptic compounds stable toward loss of trimethylaluminum, the expected main decomposition reaction. Three of the predicted lanthanide-based compounds Ln(AlMe(4))(3) (Ln = Ce, Tm, Yb) have been prepared and fully characterized in the present work, in addition to Ln(OCH(2)tBu)(3)(AlMe(3))(3) (Ln = Sc, Nd) and [Eu(AlEt(4))(2)](n). At ambient temperature, donor-free hexane solutions of Ln(AlMe(4))(3) of the Ln(3+)/Ln(2+) redox-active metal centers display enhanced reduction to [Ln(AlMe(4))(2)](n) with decreasing negative redox potential, in the order Eu ≫ Yb ≫ Sm. Whereas Eu(AlMe(4))(3) could not be identified, Yb(AlMe(4))(3) turned out to be isolable in low yield. All attempts to prepare the putative Sc(AlMe(4))(3), featuring the smallest rare earth metal center, failed.

Donor-assisted tetramethylaluminate/gallate exchange in organolanthanide complexes: pushing the limits of Pearson's HSAB concept.

La(GaMe(4))(3) and (C(5)Me(5))La(GaMe(4))(2) are obtained by reacting La(AlMe(4))(3) and (C(5)Me(5))La(AlMe(4))(2), respectively, with GaMe(3).OEt(2). Diethyl ether as a donor reverses the commonly observed Ln-GaR(4)--> Ln-AlR(4) transformation by producing the more stable AlMe(3).OEt(2), thus making homoleptic and half-sandwich tetramethylgallate complexes of the largest rare-earth metal accessible.

Homoleptic rare-earth metal(III) tetramethylaluminates: structural chemistry, reactivity, and performance in isoprene polymerization.

The complexes [Ln(AlMe4)3] (Ln=Y, La, Ce, Pr, Nd, Sm, Ho, Lu) have been synthesized by an amide elimination route and the structures of [Lu{(micro-Me)2AlMe2}3], [Sm{(micro-Me)2AlMe2}3], [Pr{(micro-Me)2AlMe2}3], and [La{(micro-Me)2AlMe2}2{(micro-Me)3AlMe}] determined by X-ray crystallography. These structures reveal a distinct Ln3+ cation size-dependency. A comprehensive insight into the intrinsic properties and solution coordination phenomena of [Ln(AlMe4)3] complexes has been gained from extended dynamic 1H and 13C NMR spectroscopic studies, as well as 1D 89Y, 2D 1H/89Y, and 27Al NMR spectroscopic investigations. [Ce(AlMe4)3] and [Pr(AlMe4)3] have been used as alkyl precursors for the synthesis of heterobimetallic alkylated rare-earth metal complexes. Both carboxylate and siloxide ligands can be introduced by methane elimination reactions that give the heterobimetallic complexes [Ln{(O2CAriPr)2(micro-AlMe2)}2(AlMe4)(C6H14)n] and [Ln{OSi(OtBu)3}(AlMe3)(AlMe4)2], respectively. [Pr{OSi(OtBu)3}(AlMe3)(AlMe4)2] has been characterized by X-ray structure analysis. All of the cerium and praseodymium complexes are used as precatalysts in the stereospecific polymerization of isoprene (1-3 equivalents of Et2AlCl as co-catalyst) and compared to the corresponding neodymium-based initiators reported previously. The superior catalytic performance of the homoleptic complexes leads to quantitative yields of high-cis-1,4-polyisoprene (>98%) in almost all of the polymerization experiments. In the case of the binary catalyst mixtures derived from carboxylate or siloxide precatalysts quantitative formation of polyisoprene is only observed for nLn:nCl=1:2. The influence of the metal size is illustrated for the heterobimetallic lanthanum, cerium, praseodymium, neodymium, and gadolinium carboxylate complexes, and the highest activities are observed for praseodymium as a metal center in the presence of one equivalent of Et2AlCl.

"Ionic carbenes": synthesis, structural characterization, and reactivity of rare-Earth metal methylidene complexes.

Treatment of mixed chloride tetramethylaluminate polynuclear clusters {Cp*Y[(mu-Me)2AlMe2](mu-Cl)}2 and {Cp*6La6[(mu-Me)3AlMe]4(mu3-Cl)2(mu2-Cl)6} with toluene/THF solutions produces "aluminum-free" methylidene complexes [Cp*3Ln3(mu-Cl)3(mu3-Cl)(mu3-CH2)(THF)3] (Ln = Y, La). The trinuclear methylidene complexes are isostructural in the solid state and feature a sterically well-shielded Schrock-type nucleophilic CH22- unit, which is prone to Tebbe-like methylenation reactions with ketones and aldehydes. The rapid polymerization of gamma-valerolactone reveals intrinsic rare-earth metal reactivity.

Multiple C-H bond activation in group 3 chemistry: synthesis and structural characterization of an yttrium-aluminum-methine cluster.

Complete donor-induced alkylaluminate cleavage of halfmetallocene complex Cp*Y(AlMe4)2, that is, treatment of Cp*Y(AlMe4)2 with 2 equiv of diethyl ether, produces [Cp*Y(mu2-Me)2]3 in high yield (95%). In contrast, the equimolar reaction of Cp*Y(AlMe4)2 with diethyl ether reproducibly formed complex [Cp*4Y4(mu2-CH3)2{(CH3)Al(mu2-CH3)2}4(mu4-CH)2] in low yield (10-30%) via a multiple C-H bond activation. The synthesis of the heterooctametallic yttrium-aluminum-methine cluster was also accomplished in moderate yield (47%) by the equimolar reaction of discrete Cp*Y(AlMe4)2 and [Cp*Y(mu2-Me)2]3 in the absence of any donor solvent and "free" AlMe3. This gives strong evidence that preformed heterometal-bridged Y-CH3-Al moieties are prone to multiple hydrogen abstraction in the presence of a highly basic reagent such as [Cp*Y(mu2-Me)2]3. The monocylopentadienyl complexes [Cp*Y(mu2-Me)2]3 and [Cp*4Y4(mu2-CH3)2{(CH3)Al(mu2-CH3)2}4(mu4-CH)2] were structurally characterized.

[LnIIAlIII2(alkyl)8]x: donor addition instead of donor-induced cleavage.

(SmAl2Me8)x and (SmAl2Et8)x are obtained via a silylamide elimination reaction from Sm[N(SiMe3)2]2(THF)2 and excess AlR3 (R = Me, Et); (LnAl2Et8)x (Ln = Sm, Yb) react with THF, pyridine, and 1,10-phenanthroline to form the first donor adducts of homoleptic peralkylated Ln-Al heterobimetallic complexes.

High tetraalkylaluminate fluxionality in half-sandwich complexes of the trivalent rare-earth metals.

Steric factors govern the formation of half-sandwich complexes (C5Me4R)Ln[N(SiHMe2)2]2 according to acid-base reactions utilising Ln[N(SiHMe2)2)3(thf)2 and substituted cyclopentadienes. Subsequent trimethylaluminium-promoted silylamide elimination produces the first half-sandwich bis(tetramethylaluminate) complexes (C5Me4R)Ln(AlMe4)2.