Neutral monocyclopentadienyllutetium alkyls: in search of steric unsaturation

Heijden, Harry van der; Pasman, P.; Boer, E.J.M. de; Schaverien, Colin J.; Orpen, A. Guy

doi:10.1021/om00108a015

Cited by 50 publications

(45 citation statements)

References 3 publications

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“…(Cp* = C 5 Me 5 ), [8] [(Cp*)LuA C H T U N G T R E N N U N G (CH 2 SiMe 3 ){CHA C H T U N G T R E N N U N G (SiMe 3 ) 2 }A C H T U N G T R E N N U N G (thf)], [8] [(Cp*)Gd-A C H T U N G T R E N N U N G (CH 2 Ph) 2 A C H T U N G T R E N N U N G (thf)], [9] [(C 5 Me 4 SiMe 2 X)YA 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)] (X = Me, Ph, C 6 F 5 ), [10] [(C 5 Me 4 SiMe 2 CH 2 CHCH 2 )YA 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) 2 ], [11] [(Cp')LnA 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)] (Ln = Sc, Gd, Dy, Lu), [3k] [{1,3-(Me 3 Si) 2 …”

Section: A C H T U N G T R E N N U N G (Thf)]mentioning

confidence: 99%

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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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Section: A C H T U N G T R E N N U N G (Thf)]mentioning

confidence: 99%

“…[8] The first structurally characterized dihydrido rare earth metal species was isolated in 2001 in a Sm…”

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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“…[8] γ-Butyrolactone is a stable, non-polymerizable cyclic ester. In this reaction, three molecules of γ-butyrolactone are completely reductively ringopened by six of the eight hydride ligands in 9 to give the linear diolate species "-O(CH 2 ) 4 O-", thus demonstrating the unusually high reactivity of this rare earth metal polyhydride complex. Further reaction between 16 and γ-butyrolactone was not observed, even when an excess amount of γ-butyrolactone was present.…”

Section: Reaction Of Rare Earth Metal Polyhydrides With Unsaturated Cmentioning

confidence: 94%

“…The reaction of 2 with 1,4-bis(trimethylsilyl)-1,3-butadiyne affords the tetranuclear yttrium tetrahydride complex 15, which formally consists of a [(C 5 Me 4 SiMe 3 )YH] 4 4+ unit and a butene-tetraanion species (Scheme 7). [8] This butenetetraanion moiety is bonded to two yttrium atoms in a π,η 4 -"inverse-sandwich" fashion and to the other two yttrium atoms in a σ 1 ,µ 1 -terminal form at the two terminal carbon atoms.…”

Section: Reaction Of Rare Earth Metal Polyhydrides With Unsaturated Cmentioning

confidence: 99%

“…A major factor that has hampered the investigation of rare earth metal dihydride or polyhydride complexes is the difficulty in isolating structurally well defined complexes. Early attempts to prepare a dihydrido rare earth metal complex by reaction of dialkyl complexes such as [(C 5 Me 5 )Lu(CH 2 CMe 3 ) 2 (THF)] [4] or [(C 5 Me 4 SiMe 3 )Y(CH 2 SiMe 3 ) 2 (THF)] [5] with H 2 did not afford a structurally characterized hydride species. The first structurally characterized dihydrido rare earth metal species was isolated as the Sm III /K heteropolymetallic form substrates including CO, CO 2 , and nitriles.…”

Section: Introductionmentioning

confidence: 99%

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Synthesis and Reactions of Polynuclear Polyhydrido Rare Earth Metal Complexes Containing “(C₅Me₄SiMe₃)LnH₂” Units: A New Frontier in Rare Earth Metal Hydride Chemistry

2007

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A series of tetranuclear octahydrido rare earth metal complexes of general formula [(C 5 Me 4 SiMe 3 )Ln(µ-H) 2 ] 4 (THF) n (Ln = Sc, Y, Gd, Dy, Ho, Er, Tm, Lu; n = 0, 1, or 2) that contain C 5 Me 4 SiMe 3 as an ancillary ligand have been prepared and structurally characterized. These hydride clusters are soluble in common organic solvents such as THF, toluene, and hexane, and maintain their tetranuclear framework in solution. Such polynuclear polyhydrido complexes exhibit extremely high and unique reactivity toward a variety of unsaturated

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Halbsandwich-Alkyl- und Hydridoyttriumkomplexe: einfache Synthese und Polymerisationskatalyse polarer Monomere

1999

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Neutral monocyclopentadienyllutetium alkyls: in search of steric unsaturation

Cited by 50 publications

References 3 publications

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

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

Synthesis and Reactions of Polynuclear Polyhydrido Rare Earth Metal Complexes Containing “(C₅Me₄SiMe₃)LnH₂” Units: A New Frontier in Rare Earth Metal Hydride Chemistry

Halbsandwich-Alkyl- und Hydridoyttriumkomplexe: einfache Synthese und Polymerisationskatalyse polarer Monomere

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Neutral monocyclopentadienyllutetium alkyls: in search of steric unsaturation

Cited by 50 publications

References 3 publications

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

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

Synthesis and Reactions of Polynuclear Polyhydrido Rare Earth Metal Complexes Containing “(C5Me4SiMe3)LnH2” Units: A New Frontier in Rare Earth Metal Hydride Chemistry

Halbsandwich-Alkyl- und Hydridoyttriumkomplexe: einfache Synthese und Polymerisationskatalyse polarer Monomere

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

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

Synthesis and Reactions of Polynuclear Polyhydrido Rare Earth Metal Complexes Containing “(C₅Me₄SiMe₃)LnH₂” Units: A New Frontier in Rare Earth Metal Hydride Chemistry