Multiple C−H Bond Activation in Group 3 Chemistry:  Synthesis and Structural Characterization of an Yttrium−Aluminum−Methine Cluster

Dietrich, H. Martin; Grove, Hilde; Törnroos, Karl W.; Anwander, Reiner

doi:10.1021/ja057618z

Cited by 92 publications

(70 citation statements)

References 31 publications

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“…[20] The most remarkable structural feature of complexes 2 is the existence of three kinds of bridging alkyl groups with a different coordination model in the core structure, which suggests the existence of at least three types of potential active sites.…”

Section: Resultsmentioning

confidence: 99%

Syntheses, Structures, and Reactivities of Homometallic Rare‐Earth‐Metal Multimethyl Methylidene and Oxo Complexes

Hong

Zhang

et al. 2011

Chemistry A European J

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Unsolvated, trinuclear, homometallic, rare-earth-metal multimethyl methylidene complexes [{(NCN)Ln(μ(2)-CH(3))}(3)(μ(3)-CH(3))(μ(3)-CH(2))] (NCN = L = [PhC{NC(6)H(4)(iPr-2,6)(2)}(2)](-); Ln = Sc (2a), Lu (2b)) have been synthesized by treatment of [(L)Ln{CH(2)C(6)H(4)N(CH(3))(2)-o}(2)] (Ln = Sc (1a), Lu (1b)) with two equivalents of AlMe(3) in toluene at ambient temperature in good yields. Treatment of 1 with three equivalents of AlMe(3) gives the heterometallic trinuclear complexes [(L)Ln(AlMe(4))(2)] (Ln = Sc (3a), Lu (3b)) in good yields. Interestingly, 2 can also be generated by recrystallization of 3 in THF/toluene, thereby indicating that the THF molecule can also induce C-H bond activation of 2. Reaction of 2 with one equivalent of ketones affords the trinuclear homometallic oxo-trimethyl complexes [{(L)Ln(μ(2) -CH(3))}(3) (μ(3)-CH(3))(μ(3)-O)] (Ln = Sc(4a), Lu(4b)) in high yields. Complex 4b reacts with one equivalent of cyclohexanone to give the methyl abstraction product [{(L)Lu(μ(2) -CH(3) )}(3) (μ(3) -OC(6)H(9))(μ(3)-O)] (5b), whereas reaction of 4b with acetophenone forms the insertion product [{(L)Lu(μ(2)-CH(3))}(3){μ(3)-OCPh(CH(3))(2)}(μ(3)-O)] (6b). Complex 4a is inert to ketone under the same conditions. All these new complexes have been characterized by elemental analysis, NMR spectroscopy, and confirmed by X-ray diffraction determination.

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Section: Resultsmentioning

confidence: 99%

Syntheses, Structures, and Reactivities of Homometallic Rare‐Earth‐Metal Multimethyl Methylidene and Oxo Complexes

Hong

Zhang

et al. 2011

Chemistry A European J

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“…(Ln = Sc, [3a] Lu [12] ), [(Cp*)ScA C H T U N G T R E N N U N G {Me 2 -A C H T U N G T R E N N U N G (O=PtBu 3 )}], [13] [{(Cp*)YA C H T U N G T R E N N U N G (m 2 -Me) 2 } 3 ], [14] and [{C 5 Me 4 SiMe 2 -A C H T U N G T R E N N U N G (C 4 H 3 O-2)}LuA C H T U N G T R E N N U N G (CH 2 SiMe 3 ) 2 A C H T U N G T R E N N U N G (thf)]. [15] In addition to these alkyl ligands, o-dimethylaminobenzyl has also been found useful for stabilization of the analogous half-sandwich complexes such as [(Cp')Sc(CH 2 C 6 H 4 NMe 2 -o) 2 ] [3f] and [(2,5-tBu 2 C 4 H 2 N)Ln(CH 2 C 6 H 4 NMe 2 -o) 2 ] (Ln= Sc, Y, La).…”

Section: H 3 }Sca C H T U N G T R E N N U N G (Ch 2 Sime 3 ) 2 a mentioning

confidence: 99%

Synthesis and Structures of the C₅Me₄SiMe₃‐Supported Polyhydride Complexes over the Full Size Range of the Rare Earth Series

Nishiura

Baldamus

Shima

et al. 2011

Chemistry A European J

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The acid-base reaction of [Ln(CH(2)SiMe(3))(3)(thf)(2)] with Cp'H gave the corresponding half-sandwich rare earth dialkyl complexes [(Cp')Ln(CH(2)SiMe(3))(2)(thf)] (1-Ln: Ln=Sc, Y, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu; Cp'=C(5)Me(4)SiMe(3)) in 62-90% isolated yields. X-ray crystallographic studies revealed that all of these complexes adopt a similar overall structure, in spite of large difference in metal-ion size. In most cases, the hydrogenolysis of the dialkyl complexes in toluene gave the tetranuclear octahydride complexes [{(Cp')Ln(μ-H)(2)}(4)(thf)(x)] (2-Ln: Ln=Sc, x=0; Y, x=1; Er, x=1; Tm, x=1; Gd, x=1; Dy, x=1; Ho, x=1) as the only isolable product. However, in the case of Lu, a trinuclear pentahydride [(Cp')(2)Lu(3)(μ-H)(5)(μ-CH(2)SiMe(2)C(5)Me(4))(thf)(2)] (3), in which the C-H activation of a methyl group of the Me(3)Si unit on a Cp' ligand took place, was obtained as a major product (66% yield), in addition to the tetranuclear octahydride [{(Cp')Lu(μ-H)(2)}(4)(thf)] (2-Lu, 34%). The use of hexane instead of toluene as a solvent for the hydrogenolysis of 1-Lu led to formation of 2-Lu as a major product (85%), while a similar reaction in THF yielded 3 predominantly (90%). The tetranuclear octahydride complexes of early (larger) lanthanide metals [{Cp'Ln(μ-H)(2)}(4)(thf)(2)] (2, Ln=La, Ce, Pr, Nd, Sm) were obtained in 38-57% isolated yields by hydrogenolysis of the bis(aminobenzyl) species [Cp'Ln(CH(2)C(6)H(4)NMe(2)-o)(2)], which were generated in-situ by reaction of [Ln(CH(2)C(6)H(4)NMe(2)-o)(3)] with one equivalent of Cp'H. X-ray crystallographic studies showed that the fine structures of these hydride clusters are dependent on the size of the metal ions.

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“…Efforts in this area were initiated by Pearce and Lappert, who reported Cp2M(-Me)2AlR2 (R = Me and M = Sc, Gd, Dy, Ho, Er, Tm, or Yb; R = Et and M = Sc or Y) (Ballard and Pearce, 1975;Holton et al, 1976), and were continued by Anwander (Fischbach and 14 Anwander, 2006), who developed homoleptic tetraalkylaluminate rare earth complexes Occhipinti et al, 2011) and bridging methylidenes (Dietrich et al, 2006b) and methylidynes (Dietrich et al, 2006a) as part of rare earth aluminum small clusters. Interestingly, the crystal structures of isostructural bridging hexacoordinate carbides, (…”

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confidence: 99%

Rare Earth Arene-Bridged Complexes Obtained by Reduction of Organometallic Precursors

Huang

Diaconescu

2014

Including Actinides

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Rare earth chemistry has witnessed remarkable advances in recent years. In particular, ancillary ligands other than cyclopentadienyl derivatives have been introduced to the organometallic chemistry and their complexes exhibit distinct reactivity and properties compared to the metallocene or half-sandwiched analogues. The present chapter reviews arene-bridged rare earth complexes with an emphasis on those compounds obtained by reduction reactions. A particular emphasis is placed on rare earth complexes supported by 1,1′-ferrocenediyl diamides since they show the most diverse chemistry with arenes: fused arenes, such as naphthalene and anthracene, formed inverse-sandwiched complexes, in which the arene is dianionic; weakly conjugated arenes, such as biphenyl, p-terphenyl, and 1,3,5-triphenylbenzene, were unexpectedly reduced by four electrons and led to 6-carbon, 10- electron aromatic systems; on the contrary, (E)-stilbene, which has a carbon-carbon double bond between the two phenyl rings, could only be reduced by two electrons, which were located on the carbon-carbon double bond instead of the phenyl rings.

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Multiple C−H Bond Activation in Group 3 Chemistry: Synthesis and Structural Characterization of an Yttrium−Aluminum−Methine Cluster

Cited by 92 publications

References 31 publications

Syntheses, Structures, and Reactivities of Homometallic Rare‐Earth‐Metal Multimethyl Methylidene and Oxo Complexes

Syntheses, Structures, and Reactivities of Homometallic Rare‐Earth‐Metal Multimethyl Methylidene and Oxo Complexes

Synthesis and Structures of the C₅Me₄SiMe₃‐Supported Polyhydride Complexes over the Full Size Range of the Rare Earth Series

Rare Earth Arene-Bridged Complexes Obtained by Reduction of Organometallic Precursors

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Multiple C−H Bond Activation in Group 3 Chemistry: Synthesis and Structural Characterization of an Yttrium−Aluminum−Methine Cluster

Cited by 92 publications

References 31 publications

Syntheses, Structures, and Reactivities of Homometallic Rare‐Earth‐Metal Multimethyl Methylidene and Oxo Complexes

Syntheses, Structures, and Reactivities of Homometallic Rare‐Earth‐Metal Multimethyl Methylidene and Oxo Complexes

Synthesis and Structures of the C5Me4SiMe3‐Supported Polyhydride Complexes over the Full Size Range of the Rare Earth Series

Rare Earth Arene-Bridged Complexes Obtained by Reduction of Organometallic Precursors

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Synthesis and Structures of the C₅Me₄SiMe₃‐Supported Polyhydride Complexes over the Full Size Range of the Rare Earth Series