Half‐Sandwich o‐N,N‐Dimethylaminobenzyl Complexes over the Full Size Range of Group 3 and Lanthanide Metals. Synthesis, Structural Characterization, and Catalysis of Phosphine PH Bond Addition to Carbodiimides

Zhang, Wen‐Xiong; Nishiura, Masayoshi; Mashiko, T.; Hou, Zhaomin

doi:10.1002/chem.200701300

Cited by 104 publications

(83 citation statements)

References 46 publications

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“…Five years after the report on the syntheses and structures of La(DMA) 3 and Y(DMA) 3 [10], many intermediate members in the Ln(DMA) 3 family have been prepared and were shown to form isomorphous crystals [12][13][14]. Although this series of complexes is not as reactive as the unstabilized Ln(Bn) 3 complexes, they are reactive enough for further functionalization (vide infra).…”

Section: Methodsmentioning

confidence: 99%

“…This increased the crystalline yield from 41 % up to 87 % and gave good yields for other metals like Pr and Nd (92 % and 83 %, respectively) [14]. It was further found that reaction of LnCl 3 precursors with Li(DMA) also gave satisfactory crystalline yields for the metals Y (75 %), Sm (92 %), Gd (85 %) and Lu (77 %) [14]. Also Xie et al report that Y(DMA) 3 and Er(DMA) 3 have been prepared from LnCl 3 and Li(DMA) in yields of 81 % and 55 %, respectively [20].…”

Section: Synthesesmentioning

confidence: 96%

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Benzyllanthanide Chemistry: Revival of Manzer’s ortho‐Me₂N‐Benzyl Ligand

Harder¹

2010

Zeitschrift anorg allge chemie

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The Manzer benzyl ligand, ortho-Me 2 N-benzyl (DMA), has been introduced in lanthanide (Ln) chemistry more than three decades ago with the syntheses of Sc(DMA) 3 and Er(DMA) 3 but no reaction chemistry or structures have been described. Only recently it was shown that a Ln(DMA) 3 complex can also be obtained for the largest Ln metal La and first crystal structures appeared. At present crystal structures of many Ln(DMA) 3 complexes throughout the series have been determined and were found to be isomorphous. This reports describes the improvement of synthetic methods for Ln(DMA) 3 complexes, a discussion on structures and trends and more important, the wide scope of Ln(DMA) 3 reagents as versatile building-blocks in lanthanide chemistry: the fast-growing number of complexes and catalysts that have been made starting from a Ln(DMA) 3 reagent are summarized. Despite the intramolecular chelating Me 2 N-arm, half-sandwich catalysts containing the DMA fragment are still active in alkene polymerizations or other catalytic conversions. The main advantages of Ln(DMA) 3 complexes are: i) easy syntheses from commercially available starting materials, ii) convenient crystallization which warrants high purity, iii) high stability on account of intramolecular coordination while sufficient reactivity for further conversions is maintained and iv) availability of these reagents over the full Ln range which is advantageous for catalyst screening.

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Section: Methodsmentioning

confidence: 99%

Section: Synthesesmentioning

confidence: 96%

Benzyllanthanide Chemistry: Revival of Manzer’s ortho‐Me₂N‐Benzyl Ligand

Harder¹

2010

Zeitschrift anorg allge chemie

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“…In most cases, the desired complexes [Ln(CH 2 C 6 H 4 NMe 2 -o){Me 2 Si(C 5 Me 4 )-(NC 6 H 2 Me 3 -2,4,6)}(thf)] (13-Ln: Ln = Y, La, Pr, Nd, Sm, Gd, and Lu) can be easily prepared by the reaction of [Ln(CH 2 C 6 H 4 NMe 2 -o) 3 ] with the corresponding cyclopentadienylamine ligands (Scheme 23). 26 However, in the case of scandium (13-Sc) (the smallest ion in the rare earth series), the one-pot metathetical reactions of ScCl 3 (thf) 3 with 1 equivalent of the dilithium salt of the ligand and 1 equivalent of LiCH 2 C 6 H 4 NMe 2 -o prove to be a more appropriate synthetic route (Scheme 23). 26 …”

Section: 25mentioning

confidence: 99%

“…26 However, in the case of scandium (13-Sc) (the smallest ion in the rare earth series), the one-pot metathetical reactions of ScCl 3 (thf) 3 with 1 equivalent of the dilithium salt of the ligand and 1 equivalent of LiCH 2 C 6 H 4 NMe 2 -o prove to be a more appropriate synthetic route (Scheme 23). 26 …”

Section: 25mentioning

confidence: 99%

“…The half-sandwich rare earth metal aminobenzyl complexes (13-La, -Pr, -Nd, -Sm, -Gd, and -Lu) serve as efficient catalysts for the addition of phosphine PH bonds to carbodiimides to afford a new family of phosphaguanidines with various substituents (Scheme 33). 26 The catalytic activity of these complexes increases as the metal size becomes larger (La > Pr > Nd > Sm > Gd > Lu), and therefore, the largest lanthanum complex 13-La shows the highest activity. A wide range of arylphosphines can be used as the nucleophiles.…”

Section: Catalytic Addition Of Terminalmentioning

confidence: 99%

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Half-Sandwich Rare Earth Metal Complexes as Novel Catalysts for Olefin Polymerization and Other Chemical Transformations

Nishiura

Hou

2010

Bulletin of the Chemical Society of Japan

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This article describes our recent studies on the synthesis and chemistry of mono(cyclopentadienyl)-ligated rare earth metal alkyl and hydride complexes. The half-sandwich mono-and dialkyl rare earth metal complexes are prepared either by alkane elimination reactions between trialkyl rare earth complexes and the neutral cyclopentadiene derivatives or by metathetical reactions of rare earth trichlorides with the alkali metal salts of the corresponding ligands. 4 ] generates easily the corresponding cationic monoalkyl species, which serve as excellent catalysts for the polymerization and copolymerization of a variety of olefins to yield a new family of polymer materials that show novel properties but are difficult to prepare by other catalysts. The half-sandwich monoalkyl rare earth complexes bearing the silylene-linked cyclopentadienylarylamido ligands act as excellent catalysts for the catalytic dimerization of terminal alkynes, cross coupling of terminal alkynes with isocyanides, and the catalytic addition of terminal alkyne CH, amine NH, and phosphine PH bonds to carbodiimides. The hydrogenolysis of the dialkyl rare earth complexes with H 2 affords a new class of polynuclear rare earth metal polyhydride complexes, which show unique features in both structure and reactivity.

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