Rare-Earth Metal Alkyl and Hydride Complexes Stabilized by a Cyclen-Derived [NNNN] Macrocyclic Ancillary Ligand

Ohashi, Masato; Konkol, Marcin; Rosal, Iker del; Poteau, Romuald; Maron, Laurent; Okuda, Jun

doi:10.1021/ja801771u

Cited by 100 publications

(63 citation statements)

References 30 publications

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“…The hydride chemical shifts are at lower fields than those observed in [(Me 3 TACD)LnH 2 ] 3 (Y, 6.37 (m) and Lu, 9.81 (s) ppm) [16], however the chemical shift difference between the Y and Lu hydrides remains relatively constant at ca. 3.5 ppm.…”

Section: Rational Approach: [(Tp Ipr2 )Lnh 2 ] 3 (Ln ¼ Y Lu) Complexesmentioning

confidence: 70%

“…More recently, Okuda and coworkers described trinuclear, [(Me 3 TACD)LnH 2 ] 3 complexes (Me 3 TACDH ¼ 1,4,7-trimethyl-1,4,7,10-tetraazacylododecane; Ln ¼ Y, Ho, Lu) [16], and Kempe, Trifonov and coworkers disclosed the synthesis of trinuclear alkylpentahydrides, [(Ap*Ln) 3 H 5 (CH 2 SiMe 3 )(THF) 2 ] (Ap*H¼ (2,6-diisopropylphenyl)[6-(2,4,6-triisopropylphenyl)pyridine-2-yl]amine; Ln ¼ Y, Lu) [17].…”

Section: Introductionmentioning

confidence: 99%

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Variable nuclearity scorpionate-supported lanthanide polyhydrides: [(TpR,R′)LnH2]n (n=3, 4 and 6)

Cheng

Saliu

Ferguson

et al. 2010

Journal of Organometallic Chemistry

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Section: Rational Approach: [(Tp Ipr2 )Lnh 2 ] 3 (Ln ¼ Y Lu) Complexesmentioning

confidence: 70%

Section: Introductionmentioning

confidence: 99%

Variable nuclearity scorpionate-supported lanthanide polyhydrides: [(TpR,R′)LnH2]n (n=3, 4 and 6)

Cheng

Saliu

Ferguson

et al. 2010

Journal of Organometallic Chemistry

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“…[17,18] More recently, rare earth polyhydride complexes with multidentate non-Cp ligands, such as [{(TpMe 2 )LnA C H T U N G T R E N N U N G (m-H) 2 } 4 ] (Ln= Y, Nd, Sm, Lu; TpMe 2 = tris(3,5-dimethylpyrazolyl)borate), [19] [{LnA C H T U N G T R E N N U N G (Me 3 TACD)H 2 } 3 ] (Ln = Y, Ho, Lu; Me 3 TACDH = 1,4,7-trimethyl-1,4,7,10-tetraazacyclododecane), [20] and [(Ap*Ln) 3 [21] were also reported. However, the rare earth polyhydride complexes reported so far in the literature were limited to those of smaller metal ions, whereas polyhydride complexes of the largest early lanthanide metals such as La, Ce, and Pr have not been reported previously.…”

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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“…[3] The metal complexes are obtained from an alkyl lanthanide precursor and the polyamine under metalation of the secondary amine group. A common route to metal complexes is salt metathesis starting from the metalated macrocyclic ligand (usually lithium is used).…”

Section: Introductionmentioning

confidence: 99%

Lithiation of a Cyclen‐Derived (NNNN) Macrocycle and Its Reaction with n‐Butyllithium

2010

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Cyclic polyamine 1,4,7‐trimethyl‐1,4,7,10‐tetraazacyclododecane, (Me3TACD)H (1), was metalated with n‐butyllithium in pentane to give [Li2(Me3TACD)2] (2). The structure of this compound is dimeric in the solid state as shown by single‐crystal X‐ray diffraction. With an excess of nBuLi, nBuLi is incorporated into the product. Depending on the stoichiometry, the compounds [Li3(nBu)(Me3TACD)2] (3) or [Li4(nBu)2(Me3TACD)2] (4) are formed. As shown by single‐crystal X‐ray diffraction, both molecular structures show a ladder motif. (Me3TACD)H reacted with NaI/Na2CO3 in acetonitrile to give benzene‐soluble [NaI(Me3TACD)H] (5).

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Rare-Earth Metal Alkyl and Hydride Complexes Stabilized by a Cyclen-Derived [NNNN] Macrocyclic Ancillary Ligand

Abstract: A trinuclear rare-earth metal hydride complex was synthesized from the dialkyl complex supported by a monoanionic [NNNN] macrocycle and shown to catalyze the hydrosilylation of olefins efficiently.

Cited by 100 publications

References 30 publications

Variable nuclearity scorpionate-supported lanthanide polyhydrides: [(TpR,R′)LnH2]n (n=3, 4 and 6)

Variable nuclearity scorpionate-supported lanthanide polyhydrides: [(TpR,R′)LnH2]n (n=3, 4 and 6)

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

Lithiation of a Cyclen‐Derived (NNNN) Macrocycle and Its Reaction with n‐Butyllithium

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Rare-Earth Metal Alkyl and Hydride Complexes Stabilized by a Cyclen-Derived [NNNN] Macrocyclic Ancillary Ligand

Abstract: A trinuclear rare-earth metal hydride complex was synthesized from the dialkyl complex supported by a monoanionic [NNNN] macrocycle and shown to catalyze the hydrosilylation of olefins efficiently.

Cited by 100 publications

References 30 publications

Variable nuclearity scorpionate-supported lanthanide polyhydrides: [(TpR,R′)LnH2]n (n=3, 4 and 6)

Variable nuclearity scorpionate-supported lanthanide polyhydrides: [(TpR,R′)LnH2]n (n=3, 4 and 6)

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

Lithiation of a Cyclen‐Derived (NNNN) Macrocycle and Its Reaction with n‐Butyllithium

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