Chloro, Alkyl and Aryl Complexes of Rare Earth Metals Supported by Bulky Tetrasubstituted Guanidinate Ligands

Lyubov, Dmitry M.; Федорова, Э. А.; Fukin, Georgy K.; Schumann, Herbert; Mühle, Stefan H.; Hummert, Markus; Bochkarev, M. N.

doi:10.1002/ejic.200500641

Cited by 48 publications

(40 citation statements)

References 53 publications

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“…These features are consistent with the symmetry observed in solution by NMR spectroscopy. The Y À O bond length in 1 a of 2.021(2) compares well with the value of 2.005 (10) found for terminal YÀO distances in the six-coordinate yttrium complex [{YCpA C H T U N G T R E N N U N G (m-OCMe 3 )A C H T U N G T R E N N U N G (OCMe 3 )} 2 ] (Cp = cyclopentadienyl). [11] A single-crystal X-ray diffraction study for the lutetium analogue 4 a revealed its structural similarity to 1 a (see Supporting Information; Figure S1).…”

Section: Resultssupporting

confidence: 54%

“…The Y À N bond lengths in 1 a are very similar (2.325(3)-2.374(2) ) and are comparable to those reported for related bis(guanidinate)-yttrium complexes. [10] The NÀC bond lengths in the guanidinate ligands differ only slightly from each other (1.328(4)-1.335(4) ), reflecting electron delocalization within the anionic NCN units. These features are consistent with the symmetry observed in solution by NMR spectroscopy.…”

Section: Resultsmentioning

confidence: 99%

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Bis(guanidinate) Alkoxide Complexes of Lanthanides: Synthesis, Structures and Use in Immortal and Stereoselective Ring‐Opening Polymerization of Cyclic Esters

Ajellal

Lyubov

Sinenkov

et al. 2008

Chemistry A European J

160

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A series of new bis(guanidinate) alkoxide Group 3 metal complexes [Ln((Me3Si)2NC(NiPr)2)2(OR)] (R=OtBu, Ln=Y, Nd, Sm, Lu; R=OiPr, Ln=Y, Nd, Lu) has been synthesized. X-ray structural determinations revealed that bis(guanidinate) tert-butoxides are monomeric complexes. The isopropoxide complex [Y((Me3Si)2NC(NiPr)2)2(OiPr)] undergoes slow decomposition in solution, to afford the unusual dimeric amido complex [(Y((Me3Si)2NC(NiPr)2)2(mu-N(iPr)C triple chemical bond N))2]. Complexes [Ln((Me3Si)2NC(NiPr)2)2(OR)] (R=OtBu, Ln=Y, Nd, Sm, Lu; R=OiPr, Ln=Y, Nd, Lu) are active catalysts/initiators for the ROP of rac-lactide and rac-beta-butyrolactone under mild conditions. Most of those polymerizations proceed with a significant degree of control. Bis(guanidinate) alkoxides appear to be well suited for achieving immortal polymerization of lactide, through the introduction of large amounts of isopropanol as a chain-transfer agent. The synthesized complexes are able to promote the stereoselective ROP of rac-beta-butyrolactone to afford syndiotactic poly(hydrobutyrate) through a chain-end control mechanism, while they are surprisingly non-stereoselective for the ROP of lactide under strictly similar conditions.

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Section: Resultssupporting

confidence: 54%

Section: Resultsmentioning

confidence: 99%

Bis(guanidinate) Alkoxide Complexes of Lanthanides: Synthesis, Structures and Use in Immortal and Stereoselective Ring‐Opening Polymerization of Cyclic Esters

Ajellal

Lyubov

Sinenkov

et al. 2008

Chemistry A European J

160

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“…Several examples of alkyl complexes of rare-earth metals supported by guanidinate ligands were published recently. [31][32][33][34] We employed the advantages of the [(Me 3 Si) 2 …”

Section: Introductionmentioning

confidence: 99%

Postmetallocene Lanthanide–Hydrido Chemistry: A New Family of Complexes [{Ln{(Me₃Si)₂NC(NiPr)₂}₂(μ‐H)}₂] (Ln=Y, Nd, Sm, Gd, Yb) Supported by Guanidinate Ligands—Synthesis, Structure, and Catalytic Activity in Olefin Polymerization

Trifonov¹,

Скворцов²,

Lyubov³

et al. 2006

Chemistry A European J

Self Cite

104

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The new family of Lewis base free hydrido complexes of rare‐earth metals supported by guanidinate ligands [{Ln{(Me3Si)2NC(NiPr)2}2(μ‐H)}2] (Ln=Y, Nd, Sm, Gd, Yb) was synthesized and structurally characterized. Single‐crystal X‐ray and solution NMR studies revealed that these complexes are dimeric in both solid state and in [D6]benzene. The dimeric hydrido complexes can adopt eclipsed (Nd, Sm, Gd) or staggered (Y, Yb, Lu) conformations depending on the metal‐atom size. Catalytic activity of these [{Ln{(Me3Si)2NC(NiPr)2}2(μ‐H)}2] complexes in the polymerization of ethylene, propylene, and styrene has been investigated. Complexes of Sm and Y have high catalytic activity in ethylene polymerization (1268 and 442 g mmol−1 atm−1 h−1, respectively).

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“…Richeson 等于 1998 年首次报道了胍基稀土氯化物的合成 [172] , 之后又有多篇文献报道 [173,174] [175] 或者中性二聚体产物(图 29) [176,177] . 当配体位阻较大时, 生成中性单核氯化物 [178] .…”

Section: 基于含氮配体的稀土金属有机配合物unclassified

“…178,185,186] , 这些配合物在室温下不稳定, 但可以用于原位制备氢化物 [185] . 在 TMEDA 的存在下, 胍基稀土氯化物与 MeLi 在己烷中反应生成热稳定性较好的盐型配合物 [175,177,187] .…”

Section: β-二亚胺稀土金属有机配合物 β-二亚胺是最为重要的双齿配体unclassified

Sixty Years of the Chemistry of Rare-earth Organometallic Complexes

Changtao¹,

Wang²,

Chen³

2014

Acta Chim. Sinica

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Rare-earth elements include scandium, yttrium and fifteen lanthanides. Since Wilkinson and Birmingham reported the fist example of rare-earth organometallic complex, the chemistry of rare-earth organometallic complexes has had a great advance during the past sixty years. A variety of Cp containing rare-earth metal complexes, including mono-Cp, bis-Cp, and tri-Cp complexes, have been synthesized. Variation of the size of substituent on Cp ring, introducing the nitrogen or oxygen containing pendant arm to Cp ring or using ansa bis-Cp ligands make the synthesis and stabilization of these three types of rare-earth metal Cp complexes available. The Cp related ligands, such as indenyl and fluorenyl, also have been applied for the rare-earth organometallic complexes. From 1990's, there was a tendency to explore the rare-earth organometallic complexes with ancillary ligands beyond Cp and its derivatives in order to search for more efficient rare-earth metal catalysts. Non-Cp ligands, such as biphenolates, β-diketiminates, amidinates, guanidinates, etc. have been introduced into the chemistry of rare-earth organometallic complexes, and a larger number of non-Cp rare-earth organometallic complexes have been synthesized and characterized. The application of non-cyclopentadienyl ligands not only resulted in the rare-earth organometallic complexes with new structural features, but also the catalysts with high activity and high selectivity for the polymer synthesis and organic synthesis. The rare-earth organometallic complexes catalyze homo-and co-polymerization of olefins as well as specific polymerization of dienes and polar monomers. The discovery of the catalytic system composed of the neutral rare-earth metal dialkyls/borate enables to synthesize some interesting polymers which are difficult to be prepared by using other catalytic system. The rare-earth organometallic complexes are also able to catalyze some important organic reactions, such as hydroamination, hydrophosphinylation, and hydroalkoxylation, etc. Different from the late-translation metal catalyzed organic reactions, most of the rare-earth metal catalyzed ones do not involve oxidative addition and reductive elimination steps. The review describes some important developments of the chemistry of rare-earth organometallic complexes in the past sixty years.

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Chloro, Alkyl and Aryl Complexes of Rare Earth Metals Supported by Bulky Tetrasubstituted Guanidinate Ligands

Abstract: The reactions of anhydrous LnCl 3 (Ln = Y, Nd, Sm, Lu) with two equiv. of sodium N, NЈ-dicyclohexyl-NЈЈ-bis(trimethylsilyl)

Cited by 48 publications

References 53 publications

Bis(guanidinate) Alkoxide Complexes of Lanthanides: Synthesis, Structures and Use in Immortal and Stereoselective Ring‐Opening Polymerization of Cyclic Esters

Bis(guanidinate) Alkoxide Complexes of Lanthanides: Synthesis, Structures and Use in Immortal and Stereoselective Ring‐Opening Polymerization of Cyclic Esters

Postmetallocene Lanthanide–Hydrido Chemistry: A New Family of Complexes [{Ln{(Me₃Si)₂NC(NiPr)₂}₂(μ‐H)}₂] (Ln=Y, Nd, Sm, Gd, Yb) Supported by Guanidinate Ligands—Synthesis, Structure, and Catalytic Activity in Olefin Polymerization

Sixty Years of the Chemistry of Rare-earth Organometallic Complexes

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Chloro, Alkyl and Aryl Complexes of Rare Earth Metals Supported by Bulky Tetrasubstituted Guanidinate Ligands

Abstract: The reactions of anhydrous LnCl 3 (Ln = Y, Nd, Sm, Lu) with two equiv. of sodium N, NЈ-dicyclohexyl-NЈЈ-bis(trimethylsilyl)

Cited by 48 publications

References 53 publications

Bis(guanidinate) Alkoxide Complexes of Lanthanides: Synthesis, Structures and Use in Immortal and Stereoselective Ring‐Opening Polymerization of Cyclic Esters

Bis(guanidinate) Alkoxide Complexes of Lanthanides: Synthesis, Structures and Use in Immortal and Stereoselective Ring‐Opening Polymerization of Cyclic Esters

Postmetallocene Lanthanide–Hydrido Chemistry: A New Family of Complexes [{Ln{(Me3Si)2NC(NiPr)2}2(μ‐H)}2] (Ln=Y, Nd, Sm, Gd, Yb) Supported by Guanidinate Ligands—Synthesis, Structure, and Catalytic Activity in Olefin Polymerization

Sixty Years of the Chemistry of Rare-earth Organometallic Complexes

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Product

Resources

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Postmetallocene Lanthanide–Hydrido Chemistry: A New Family of Complexes [{Ln{(Me₃Si)₂NC(NiPr)₂}₂(μ‐H)}₂] (Ln=Y, Nd, Sm, Gd, Yb) Supported by Guanidinate Ligands—Synthesis, Structure, and Catalytic Activity in Olefin Polymerization